Block processing with bulk catalysts for base stock production from deasphalted oil

ABSTRACT

Systems and methods are provided for block operation during lubricant and/or fuels production from deasphalted oil. During “block” operation, a deasphalted oil and/or the hydroprocessed effluent from an initial processing stage can be split into a plurality of fractions. The fractions can correspond, for example, to feed fractions suitable for forming a light neutral fraction, a heavy neutral fraction, and a bright stock fraction, or the plurality of fractions can correspond to any other convenient split into separate fractions. The plurality of separate fractions can then be processed separately in the process train (or in the sweet portion of the process train) for forming fuels and/or lubricant base stocks. The initial stage can optionally include a bulk hydrotreating catalyst to assist with increasing the space velocity in the initial stage.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 62/439,943 filed Dec. 29, 2016, which is herein incorporated byreference in its entirety.

This application is related to three other co-pending U.S. applications,filed on even date herewith, and identified by the following AttorneyDocket numbers and titles: 2017EM196 entitled “Block ProcessingConfigurations For Base Stock Production From Deasphalted Oil”;2016EM406-US2 entitled “Block Processing For Base Stock Production FromDeasphalted Oil” and 2017EM195 entitled “Base Stocks And LubricantCompositions Containing Same”. Each of these co-pending U.S.applications is hereby incorporated by reference herein in its entirety.

FIELD

Systems and methods are provided for production of lubricant oil basestocks from deasphalted oils produced by low severity deasphalting ofresid fractions.

BACKGROUND

Lubricant base stocks are one of the higher value products that can begenerated from a crude oil or crude oil fraction. The ability togenerate lubricant base stocks of a desired quality is often constrainedby the availability of a suitable feedstock. For example, mostconventional processes for lubricant base stock production involvestarting with a crude fraction that has not been previously processedunder severe conditions, such as a virgin gas oil fraction from a crudewith moderate to low levels of initial sulfur content.

In some situations, a deasphalted oil formed by propane deasphalting ofa vacuum resid can be used for additional lubricant base stockproduction. Deasphalted oils can potentially be suitable for productionof heavier base stocks, such as bright stocks. However, the severity ofpropane deasphalting required in order to make a suitable feed forlubricant base stock production typically results in a yield of onlyabout 30 wt % deasphalted oil relative to the vacuum resid feed.

U.S. Pat. No. 3,414,506 describes methods for making lubricating oils byhydrotreating pentane-alcohol-deasphalted short residue. The methodsinclude performing deasphalting on a vacuum resid fraction with adeasphalting solvent comprising a mixture of an alkane, such as pentane,and one or more short chain alcohols, such as methanol and isopropylalcohol. The deasphalted oil is then hydrotreated, followed by solventextraction to perform sufficient VI uplift to form lubricating oils.

U.S. Pat. No. 7,776,206 describes methods for catalytically processingresids and/or deasphalted oils to form bright stock. A resid-derivedstream, such as a deasphalted oil, is hydroprocessed to reduce thesulfur content to less than 1 wt % and reduce the nitrogen content toless than 0.5 wt %. The hydroprocessed stream is then fractionated toform a heavier fraction and a lighter fraction at a cut point between1150° F.-1300° F. (620° C.-705° C.). The lighter fraction is thencatalytically processed in various manners to form a bright stock.

SUMMARY

In various aspects, systems and methods are provided for block operationduring lubricant and/or fuels production from deasphalted oil, such asdeasphalted oil from a solvent deasphalting process with a yield ofdeasphalted oil of at least 50 wt %. During “block” operation, adeasphalted oil and/or the hydroprocessed effluent from an initialprocessing stage can be split into a plurality of fractions. Thefractions can correspond, for example, to feed fractions suitable forforming a light neutral fraction, a heavy neutral fraction, and a brightstock fraction, or the plurality of fractions can correspond to anyother convenient split into separate fractions. The plurality ofseparate fractions can then be processed separately in the process train(or in the sweet portion of the process train) for forming fuels and/orlubricant base stocks. The initial stage can optionally include a bulkhydrotreating catalyst to assist with increasing the space velocity inthe initial stage.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically shows an example of a configuration for blockcatalytic processing of deasphalted oil to form lubricant base stocks.

FIG. 2 schematically shows an example of a configuration for blockcatalytic processing of deasphalted oil to form lubricant base stocks.

FIG. 3 schematically shows an example of a configuration for blockcatalytic processing of deasphalted oil to form lubricant base stocks.

FIG. 4 shows results from processing a pentane deasphalted oil atvarious levels of hydroprocessing severity.

FIG. 5 shows results from processing deasphalted oil in configurationswith various combinations of sour hydrocracking and sweet hydrocracking.

FIG. 6 schematically shows an example of a configuration for catalyticprocessing of a deasphalted oil to form lubricant base stocks.

FIG. 7 schematically shows an example of a configuration for blockcatalytic processing of deasphalted oil to form lubricant base stocks.

DETAILED DESCRIPTION

All numerical values within the detailed description and the claimsherein are modified by “about” or “approximately” the indicated value,and take into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

Overview

In various aspects, methods are provided for producing Group I and GroupII lubricant base stocks, including Group I and Group II bright stock,from deasphalted oils generated by low severity C₄₊ deasphalting. Lowseverity deasphalting as used herein refers to deasphalting underconditions that result in a high yield of deasphalted oil (and/or areduced amount of rejected asphalt or rock), such as a deasphalted oilyield of at least 50 wt % relative to the feed to deasphalting, or atleast 55 wt %, or at least 60 wt %, or at least 65 wt %, or at least 70wt %, or at least 75 wt %. In contrast with conventional bright stockproduced from deasphalted oil formed at low severity conditions, theGroup I and Group II bright stock described herein can be substantiallyfree from haze after storage for extended periods of time. This hazefree Group II bright stock can correspond to a bright stock with anunexpected composition.

In various additional aspects, methods are provided for catalyticprocessing of C₃ deasphalted oils to form Group II bright stock. FormingGroup II bright stock by catalytic processing can provide a bright stockwith unexpected compositional properties.

In some conventional processing schemes, a resid fraction can bedeasphalted, with the deasphalted oil used as part of a feed for forminglubricant base stocks. In conventional processing schemes a deasphaltedoil used as feed for forming lubricant base stocks is produced usingpropane deasphalting. This propane deasphalting corresponds to a “highseverity” deasphalting, as indicated by a typical yield of deasphaltedoil of roughly 40 wt % or less, and often 30 wt % or less, relative tothe initial resid fraction. In a typical lubricant base stock productionprocess, the deasphalted oil can then be solvent extracted to reduce thearomatics content, followed by solvent dewaxing to form a base stock.The low yield of deasphalted oil is based in part on the inability ofconventional methods to produce lubricant base stocks from lowerseverity deasphalting that do not form haze over time.

In some aspects, it has been discovered that lubricant base stocks canbe produced from deasphalted oil generated at high lift (i.e., highyield of deasphalted oil) while also producing base stocks that havelittle or no tendency to form haze over extended periods of time. Thedeasphalted oil can be produced by deasphalting process that uses a C₄solvent, a C₅ solvent, a C₆₊ solvent, a mixture of two or more C₄₊solvents, or a mixture of two or more C₅₊ solvents. The deasphaltingprocess can further correspond to a process with a yield of deasphaltedoil of at least 50 wt % for a vacuum resid feed having a T10distillation point (or optionally a T5 distillation point) of at least510° C., or a yield of at least 60 wt %, or at least 65 wt %, or atleast 70 wt %. It is believed that the reduced haze formation is due inpart to the reduced or minimized differential between the pour point andthe cloud point for the base stocks and/or due in part to forming abright stock with a cloud point of −5° C. or less.

In some aspects a deasphalted oil can be hydroprocessed (hydrotreatedand/or hydrocracked and/or demetallated), so that ˜700° F.+(370° C.+)conversion is 10 wt % to 40 wt %. The hydroprocessed effluent can befractionated to separate lower boiling portions from a lubricant basestock boiling range portion. The lubricant boiling range portion canthen be hydrocracked, dewaxed, and hydrofinished to produce acatalytically dewaxed effluent. Optionally but preferably, the lubricantboiling range portion can be underdewaxed, so that the wax content ofthe catalytically dewaxed heavier portion or potential bright stockportion of the effluent is at least 6 wt %, or at least 8 wt %, or atleast 10 wt %. This underdewaxing can also be suitable for forming lightor medium or heavy neutral lubricant base stocks that do not requirefurther solvent upgrading to form haze free base stocks. In thisdiscussion, the heavier portion/potential bright stock portion canroughly correspond to a 538° C.+ portion of the dewaxed effluent. Thecatalytically dewaxed heavier portion of the effluent can then besolvent dewaxed to form a solvent dewaxed effluent. The solvent dewaxedeffluent can be separated to form a plurality of base stocks with areduced tendency (such as no tendency) to form haze over time, includingat least a portion of a Group II bright stock product.

In other aspects a deasphalted oil can be hydroprocessed (hydrotreatedand/or hydrocracked and/or demetallated), so that 370° C.+ conversion isat least 40 wt %, or at least 50 wt %. The hydroprocessed effluent canbe fractionated to separate lower boiling portions from a lubricant basestock boiling range portion. The lubricant base stock boiling rangeportion can then be hydrocracked, dewaxed, and hydrofinished to producea catalytically dewaxed effluent. The catalytically dewaxed effluent canthen be solvent extracted to form a raffinate. The raffinate can beseparated to form a plurality of base stocks with a reduced tendency(such as no tendency) to form haze over time, including at least aportion of a Group I and/or Group II bright stock product.

In other aspects, it has been discovered that catalytic processing canbe used to produce Group II bright stock with unexpected compositionalproperties from C₃, C₄, C₅, and/or C₅₊ deasphalted oil. The deasphaltedoil can be hydrotreated to reduce the content of heteroatoms (such assulfur and nitrogen), followed by catalytic dewaxing under sweetconditions. Optionally, hydrocracking can be included as part of thesour hydrotreatment stage and/or as part of the sweet dewaxing stage.

Optionally, the systems and methods described herein can be used in“block” operation to allow for additional improvements in yield and/orproduct quality. During “block” operation, a deasphalted oil and/or thehydroprocessed effluent from the sour processing stage can be split intoa plurality of fractions. The fractions can correspond, for example, tofeed fractions suitable for forming a light neutral fraction, a heavyneutral fraction, and a bright stock fraction, or the plurality offractions can correspond to any other convenient split into separatefractions. The plurality of separate fractions can then be processedseparately in the process train (or in the sweet portion of the processtrain) for forming lubricant base stocks. For example, the light neutralportion of the feed can be processed for a period of time, followed byprocessing of the heavy neutral portion, followed by processing of abright stock portion. During the time period when one type of fractionis being processed, storage tanks can be used to hold the remainingfractions.

Block operation can allow the processing conditions in the process trainto be tailored to each type of lubricant fraction. For example, theamount of sweet processing stage conversion of the heavy neutralfraction can be lower than the amount of sweet processing stageconversion for the light neutral fraction. This can reflect the factthat heavy neutral lubricant base stocks may not need as high aviscosity index as light neutral base stocks. In some aspects, theamount of conversion in the first (sour) stage can be 25 wt % to 75 wt%, or 30 wt % to 70 wt %, or 25 wt % to 60 wt %, or 40 wt % to 75 wt %.After blocking to form separate feeds for production of light neutralbase stock, heavy neutral base stock, and bright stock, the amount ofsecond (sweet) stage conversion can vary depending on the desiredproduct. For light neutral production, the amount of second stageconversion can be 15 wt % to 50 wt %. For heavy neutral production, thesecond stage conversion can be 5 wt % to 25 wt %. For bright stockproduction, the second stage conversion can be 40 wt % to 70 wt %.Optionally, the amount of conversion for the light neutral can be atleast 10 wt % greater than the amount of conversion for the heavyneutral, or at least 15 wt % greater. Optionally, the amount ofconversion for the bright stock can be at least 10 wt % greater than theamount of conversion for any light neutral or heavy neutral base stocksderived from blocking of a single feed, or at least 20 wt % greater.

Another option for modifying the production of base stocks can be torecycle a portion of at least one lubricant base stock product forfurther processing in the process train. This can correspond torecycling a portion of a base stock product for further processing inthe sour stage and/or recycling a portion of a base stock product forfurther processing in the corresponding sweet stage. Optionally, a basestock product can be recycled for further processing in a differentphase of block operation, such as recycling light neutral base stockproduct formed during block processing of the heavy neutral fraction forfurther processing during block processing of the light neutralfraction. The amount of base stock product recycled can correspond toany convenient amount of a base stock product effluent from thefractionator, such as 1 wt % to 50 wt % of a base stock producteffluent, or 1 wt % to 20 wt %.

Recycling a portion of a base stock product effluent can optionally beused while operating a lube processing system at higher than typicallevels of fuels conversion. When using a conventional feed for lubricantproduction, total conversion of feed relative to 370° C. can be limitedto 65 wt % or less. Conversion of more than 65 wt % of a feed relativeto 370° C. is typically not favored due to loss of viscosity index withadditional conversion. At elevated levels of conversion, the loss of VIwith additional conversion is believed to be due to cracking and/orconversion of isoparaffins within a feed. For feeds derived fromdeasphalted oil, however, the amount of isoparaffins within a feed islower than a conventional feed. As a result, additional conversion canbe performed without loss of VI. In some aspects, converting at least 70wt % of a feed, or at least 75 wt %, or at least 80 wt % can allow forproduction of lubricant base stocks with substantially improved coldflow properties while still maintaining the viscosity index of theproducts at a similar value to the viscosity index at a conventionalconversion of 60 wt %.

In various aspects, a variety of combinations of catalytic and/orsolvent processing can be used to form lubricant base stocks, includingGroup II bright stock, from deasphalted oils. These combinationsinclude, but are not limited to:

a) Hydroprocessing of a deasphalted oil under sour conditions (i.e.,sulfur content of at least 500 wppm); separation of the hydroprocessedeffluent to form at least a lubricant boiling range fraction; andcatalytic dewaxing of the lubricant boiling range fraction under sweetconditions (i.e., 500 wppm or less sulfur). The catalytic dewaxing canoptionally correspond to catalytic dewaxing using a dewaxing catalystwith a pore size greater than 8.4 Angstroms. Optionally, the sweetprocessing conditions can further include hydrocracking, noble metalhydrotreatment, and/or hydrofinishing. The optional hydrocracking, noblemetal hydrotreatment, and/or hydrofinishing can occur prior to and/orafter or after catalytic dewaxing. For example, the order of catalyticprocessing under sweet processing conditions can be noble metalhydrotreating followed by hydrocracking followed by catalytic dewaxing.

b) The process of a) above, followed by performing an additionalseparation on at least a portion of the catalytically dewaxed effluent.The additional separation can correspond to solvent dewaxing, solventextraction (such as solvent extraction with furfural orn-methylpyrollidone), a physical separation such as ultracentrifugation,or a combination thereof.

Group I base stocks or base oils are defined as base stocks with lessthan 90 wt % saturated molecules and/or at least 0.03 wt % sulfurcontent. Group I base stocks also have a viscosity index (VI) of atleast 80 but less than 120. Group II base stocks or base oils contain atleast 90 wt % saturated molecules and less than 0.03 wt % sulfur. GroupII base stocks also have a viscosity index of at least 80 but less than120. Group III base stocks or base oils contain at least 90 wt %saturated molecules and less than 0.03 wt % sulfur, with a viscosityindex of at least 120.

In some aspects, a Group III base stock as described herein maycorrespond to a Group III+base stock. Although a generally accepteddefinition is not available, a Group III+base stock can generallycorrespond to a base stock that satisfies the requirements for a GroupIII base stock while also having at least one property that is enhancedrelative to a Group III specification. The enhanced property cancorrespond to, for example, having a viscosity index that issubstantially greater than the required specification of 120, such as aGroup III base stock having a VI of at least 130, or at least 135, or atleast 140. Similarly, in some aspects, a Group II base stock asdescribed herein may correspond to a Group II+base stock. Although agenerally accepted definition is not available, a Group II+base stockcan generally correspond to a base stock that satisfies the requirementsfor a Group II base stock while also having at least one property thatis enhanced relative to a Group II specification. The enhanced propertycan correspond to, for example, having a viscosity index that issubstantially greater than the required specification of 80, such as aGroup II base stock having a VI of at least 103, or at least 108, or atleast 113.

In the discussion below, a stage can correspond to a single reactor or aplurality of reactors. Optionally, multiple parallel reactors can beused to perform one or more of the processes, or multiple parallelreactors can be used for all processes in a stage. Each stage and/orreactor can include one or more catalyst beds containing hydroprocessingcatalyst. Note that a “bed” of catalyst in the discussion below canrefer to a partial physical catalyst bed. For example, a catalyst bedwithin a reactor could be filled partially with a hydrocracking catalystand partially with a dewaxing catalyst. For convenience in description,even though the two catalysts may be stacked together in a singlecatalyst bed, the hydrocracking catalyst and dewaxing catalyst can eachbe referred to conceptually as separate catalyst beds.

In this discussion, conditions may be provided for various types ofhydroprocessing of feeds or effluents. Examples of hydroprocessing caninclude, but are not limited to, one or more of hydrotreating,hydrocracking, catalytic dewaxing, and hydrofinishing/aromaticsaturation. Such hydroprocessing conditions can be controlled to havedesired values for the conditions (e.g., temperature, pressure, LHSV,treat gas rate) by using at least one controller, such as a plurality ofcontrollers, to control one or more of the hydroprocessing conditions.In some aspects, for a given type of hydroprocessing, at least onecontroller can be associated with each type of hydroprocessingcondition. In some aspects, one or more of the hydroprocessingconditions can be controlled by an associated controller. Examples ofstructures that can be controlled by a controller can include, but arenot limited to, valves that control a flow rate, a pressure, or acombination thereof; heat exchangers and/or heaters that control atemperature; and one or more flow meters and one or more associatedvalves that control relative flow rates of at least two flows. Suchcontrollers can optionally include a controller feedback loop includingat least a processor, a detector for detecting a value of a controlvariable (e.g., temperature, pressure, flow rate, and a processor outputfor controlling the value of a manipulated variable (e.g., changing theposition of a valve, increasing or decreasing the duty cycle and/ortemperature for a heater). Optionally, at least one hydroprocessingcondition for a given type of hydroprocessing may not have an associatedcontroller.

In this discussion, unless otherwise specified a lubricant boiling rangefraction corresponds to a fraction having an initial boiling point oralternatively a T5 boiling point of at least about 370° C. (˜700° F.). Adistillate fuel boiling range fraction, such as a diesel productfraction, corresponds to a fraction having a boiling range from about193° C. (375° F.) to about 370° C. (˜700° F.). Thus, distillate fuelboiling range fractions (such as distillate fuel product fractions) canhave initial boiling points (or alternatively T5 boiling points) of atleast about 193° C. and final boiling points (or alternatively T95boiling points) of about 370° C. or less. A naphtha boiling rangefraction corresponds to a fraction having a boiling range from about 36°C. (122° F.) to about 193° C. (375° F.) to about 370° C. (˜700° F.).Thus, naphtha fuel product fractions can have initial boiling points (oralternatively T5 boiling points) of at least about 36° C. and finalboiling points (or alternatively T95 boiling points) of about 193° C. orless. It is noted that 36° C. roughly corresponds to a boiling point forthe various isomers of a C5 alkane. A fuels boiling range fraction cancorrespond to a distillate fuel boiling range fraction, a naphthaboiling range fraction, or a fraction that includes both distillate fuelboiling range and naphtha boiling range components. Light ends aredefined as products with boiling points below about 36° C., whichinclude various C1-C4 compounds. When determining a boiling point or aboiling range for a feed or product fraction, an appropriate ASTM testmethod can be used, such as the procedures described in ASTM D2887,D2892, and/or D86. Preferably, ASTM D2887 should be used unless a sampleis not appropriate for characterization based on ASTM D2887. Forexample, for samples that will not completely elute from achromatographic column, ASTM D7169 can be used.

Process Variations

In various aspects, hydroprocessing of deasphalted oil to form lubricantbase stocks can result in formation of a variety of products. Inaddition to light neutral, heavy neutral, and bright stock productsformed by block processing, additional fuels and lubricant products canbe formed. The fuels products can include naphtha and diesel fractionsformed due to conversion in the sour stage and conversion in the sweetstage. The sour stage fuels products can optionally be processedfurther, if necessary, in order to satisfy desired standards for sulfurand nitrogen content. The additional lubricant products can includeadditional light neutral and heavy neutral products that are formedduring block processing. For example, sweet stage processing of theheavy neutral block feed can result in some “conversion” of heavyneutral base stock to light neutral base stock. Similarly, sweet stageprocessing of the bright stock block feed can result in some“conversion” of bright stock to light neutral base stock and/or heavyneutral base stock.

In some aspects, alternative types of products and/or productdispositions can be generated in conjunction with hydroprocessing of adeasphalted oil. For example, various sour stage and/or sweet stageeffluents can be suitable for use as a steam cracker feed. Both the sourstage hydrocrackate and the basestock products, particularly the heavydiesel and naphtha, and/or any narrow boiling range fractions that maybe distilled in between lube cuts to manage lube properties, can makesuitable steam cracker feeds. It could be a single component, a blend ofa few components, or the entire sour stage product which may be sent toa steam cracker. Such a steam cracker feed can have 98 wt % or moresaturates for the sweet products and 75 wt % or more saturates for thehydrocrackates, which can be beneficial in a steam cracker feed.Additionally, such a feed can be low in sulfur which can reduce orminimize tar formation.

As another example, the bright stock product can be used as anunexpectedly beneficial fluxant for asphalt production. The bright stockis sufficiently heavy to avoid mass loss, has low viscosity, andalthough the saturates content is relatively high, because it is dewaxedit has very low wax. Wax is a detrimental quality for asphalt, and mostlow viscosity fluxes for asphalt type streams that are also non-toxic,like vacuum gas oils, have significant quantities of wax. This can makea bright stock made according to the processes described herein asuitable flux for a high asphaltene, high viscosity asphalt blendcomponent, such as deasphalter rock, or deasphalter rock from ahigh-lift deasphalter.

In various aspects, the sweet stage of the reaction system can include ahydrocracking catalyst followed (downstream) by a dewaxing catalystfollowed by an aromatic saturation catalyst. For example, the sweetstage of a reaction system can include a first reactor containinghydrocracking catalyst, a second reactor containing dewaxing catalyst,and a third reactor containing aromatic saturation catalyst. In someaspects, other types of catalyst configurations in the sweet stage canbe beneficial.

As an example, the first reactor in the sweet stage can include ahydrocracking catalyst followed by an aromatic saturation catalyst.Including both hydrocracking and aromatic saturation functionality inthe initial part of the sweet stage can be beneficial for allowingboiling point conversion and/or viscosity index upgrading that can betailored for each type of blocked feed. Because this reactor is a sweetprocessing stage, the temperature can be relatively low, thus allowingeffective aromatic saturation (reduced amount of constraint due toequilibrium) while still being able to achieve desired boiling pointconversion and/or viscosity index upgrading.

As another example, the initial reactor or portion of the sweet stagecan include an aromatic saturation catalyst without the presence of ahydrocracking catalyst. This type of configuration can provide superioryield for basestocks that do not require additional viscosity indexupgrade in the sweet stage. Additionally or alternately, at end of run,the lack of a hydrocracking catalyst can allow the sweet stage reactors(or at least the initial reactor) to be operated to be operated athigher temperature to achieve desired aromatic saturation withoutexcessive cracking.

In various aspects, the sour stage of the reaction system can includeone or more optional demetallization catalysts followed (downstream) bya hydrotreating catalyst followed by a hydrocracking catalyst. In someaspects, a large pore catalyst, such as a demetallization catalyst, canbe included downstream from the hydrocracking catalyst. Such a largepore catalyst downstream from the hydrocracking catalyst can bebeneficial due to the differences between a feed corresponding to a highyield deasphalted oil and a conventional feed for lubricant production.During processing of a conventional feed for lubricant production,removal of mercaptans can potentially pose a challenge at the end of asour stage. A conventional hydrotreating catalyst after a hydrocrackingcatalyst can be suitable for removal of such mercaptans. For a feedbased on a deasphalted oil, the substantially higher percentage ofmulti-ring structures in the feed can result in formation of polynucleararomatics during hydrocracking. Such polynuclear aromatics are not asreadily treated using a conventional hydrotreating catalyst. However,the larger pore size of a demetallization catalyst (such as 200 nm orgreater median pore size) can be allow demetallization catalysts to beeffective for saturation of polynuclear aromatics. Such demetallizationcatalysts can also be effective for mercaptan removal.

Feedstocks

In various aspects, at least a portion of a feedstock for processing asdescribed herein can correspond to a vacuum resid fraction or anothertype 950° F.+(510° C.+) or 1000° F.+(538° C.+) fraction. Another exampleof a method for forming a 950° F.+(510° C.+) or 1000° F.+(538° C.+)fraction is to perform a high temperature flash separation. The 950°F.+(510° C.+) or 1000° F.+(538° C.+) fraction formed from the hightemperature flash can be processed in a manner similar to a vacuumresid.

A vacuum resid fraction or a 950° F.+(510° C.+) fraction formed byanother process (such as a flash fractionation bottoms or a bitumenfraction) can be deasphalted at low severity to form a deasphalted oil.Optionally, the feedstock can also include a portion of a conventionalfeed for lubricant base stock production, such as a vacuum gas oil.

A vacuum resid (or other 510° C.+) fraction can correspond to a fractionwith a T5 distillation point (ASTM D2892, or ASTM D7169 if the fractionwill not completely elute from a chromatographic system) of at leastabout 900° F. (482° C.), or at least 950° F. (510° C.), or at least1000° F. (538° C.). Alternatively, a vacuum resid fraction can becharacterized based on a T10 distillation point (ASTM D2892/D7169) of atleast about 900° F. (482° C.), or at least 950° F. (510° C.), or atleast 1000° F. (538° C.).

Resid (or other 510° C.+) fractions can be high in metals. For example,a resid fraction can be high in total nickel, vanadium and ironcontents. In an aspect, a resid fraction can contain at least 0.00005grams of Ni/V/Fe (50 wppm) or at least 0.0002 grams of Ni/V/Fe (200wppm) per gram of resid, on a total elemental basis of nickel, vanadiumand iron. In other aspects, the heavy oil can contain at least 500 wppmof nickel, vanadium, and iron, such as up to 1000 wppm or more.

Contaminants such as nitrogen and sulfur are typically found in resid(or other 510° C.+) fractions, often in organically-bound form. Nitrogencontent can range from about 50 wppm to about 10,000 wppm elementalnitrogen or more, based on total weight of the resid fraction. Sulfurcontent can range from 500 wppm to 100,000 wppm elemental sulfur ormore, based on total weight of the resid fraction, or from 1000 wppm to50,000 wppm, or from 1000 wppm to 30,000 wppm.

Still another method for characterizing a resid (or other 510° C.+)fraction is based on the Conradson carbon residue (CCR) of thefeedstock. The Conradson carbon residue of a resid fraction can be atleast about 5 wt %, such as at least about 10 wt % or at least about 20wt %. Additionally or alternately, the Conradson carbon residue of aresid fraction can be about 50 wt % or less, such as about 40 wt % orless or about 30 wt % or less.

In some aspects, a vacuum gas oil fraction can be co-processed with adeasphalted oil. The vacuum gas oil can be combined with the deasphaltedoil in various amounts ranging from 20 parts (by weight) deasphalted oilto 1 part vacuum gas oil (i.e., 20:1) to 1 part deasphalted oil to 1part vacuum gas oil. In some aspects, the ratio of deasphalted oil tovacuum gas oil can be at least 1:1 by weight, or at least 1.5:1, or atleast 2:1. Typical (vacuum) gas oil fractions can include, for example,fractions with a T5 distillation point to T95 distillation point of 650°F. (343° C.)—1050° F. (566° C.) or 650° F. (343° C.)—1000° F. (538° C.)or 650° F. (343° C.)—950° F. (510° C.), or 650° F. (343° C.)—900° F.(482° C.), or −700° F. (370° C.)—1050° F. (566° C.), or −700° F. (370°C.)—1000° F. (538° C.) or −700° F. (370° C.)—950° F. (510° C.) or −700°F. (370° C.)—900° F. (482° C.), or 750° F. (399° C.)—1050° F. (566° C.),or 750° F. (399° C.)—1000° F. (538° C.), or 750° F. (399° C.)—950° F.(510° C.), or 750° F. (399° C.)—900° F. (482° C.). For example asuitable vacuum gas oil fraction can have a T5 distillation point of atleast 343° C. and a T95 distillation point of 566° C. or less; or a T10distillation point of at least 343° C. and a T90 distillation point of566° C. or less; or a T5 distillation point of at least 370° C. and aT95 distillation point of 566° C. or less; or a T5 distillation point ofat least 343° C. and a T95 distillation point of 538° C. or less.

Solvent Deasphalting

Solvent deasphalting is a solvent extraction process. In some aspects,suitable solvents for methods as described herein include alkanes orother hydrocarbons (such as alkenes) containing 4 to 7 carbons permolecule. Examples of suitable solvents include n-butane, isobutane,n-pentane, C₄₊ alkanes, C₅₊ alkanes, C₄₊ hydrocarbons, and C₅₊hydrocarbons. In other aspects, suitable solvents can include C₃hydrocarbons, such as propane. In such other aspects, examples ofsuitable solvents include propane, n-butane, isobutane, n-pentane, C₃₊alkanes, C₄₊ alkanes, C₅₊ alkanes, C₃₊ hydrocarbons, C₄₊ hydrocarbons,and C₅₊ hydrocarbons

In this discussion, a solvent comprising C_(n) (hydrocarbons) is definedas a solvent composed of at least 80 wt % of alkanes (hydrocarbons)having n carbon atoms, or at least 85 wt %, or at least 90 wt %, or atleast 95 wt %, or at least 98 wt %. Similarly, a solvent comprisingC_(n+) (hydrocarbons) is defined as a solvent composed of at least 80 wt% of alkanes (hydrocarbons) having n or more carbon atoms, or at least85 wt %, or at least 90 wt %, or at least 95 wt %, or at least 98 wt %.

In this discussion, a solvent comprising C_(n) alkanes (hydrocarbons) isdefined to include the situation where the solvent corresponds to asingle alkane (hydrocarbon) containing n carbon atoms (for example, n=3,4, 5, 6, 7) as well as the situations where the solvent is composed of amixture of alkanes (hydrocarbons) containing n carbon atoms. Similarly,a solvent comprising C_(n+) alkanes (hydrocarbons) is defined to includethe situation where the solvent corresponds to a single alkane(hydrocarbon) containing n or more carbon atoms (for example, n=3, 4, 5,6, 7) as well as the situations where the solvent corresponds to amixture of alkanes (hydrocarbons) containing n or more carbon atoms.Thus, a solvent comprising C₄₊ alkanes can correspond to a solventincluding n-butane; a solvent include n-butane and isobutane; a solventcorresponding to a mixture of one or more butane isomers and one or morepentane isomers; or any other convenient combination of alkanescontaining 4 or more carbon atoms. Similarly, a solvent comprising C₅₊alkanes (hydrocarbons) is defined to include a solvent corresponding toa single alkane (hydrocarbon) or a solvent corresponding to a mixture ofalkanes (hydrocarbons) that contain 5 or more carbon atoms.Alternatively, other types of solvents may also be suitable, such assupercritical fluids. In various aspects, the solvent for solventdeasphalting can consist essentially of hydrocarbons, so that at least98 wt % or at least 99 wt % of the solvent corresponds to compoundscontaining only carbon and hydrogen. In aspects where the deasphaltingsolvent corresponds to a C₄₊ deasphalting solvent, the C₄₊ deasphaltingsolvent can include less than 15 wt % propane and/or other C₃hydrocarbons, or less than 10 wt %, or less than 5 wt %, or the C₄₊deasphalting solvent can be substantially free of propane and/or otherC₃ hydrocarbons (less than 1 wt %). In aspects where the deasphaltingsolvent corresponds to a C₅₊ deasphalting solvent, the C₅₊ deasphaltingsolvent can include less than 15 wt % propane, butane and/or other C₃-C₄hydrocarbons, or less than 10 wt %, or less than 5 wt %, or the C₅₊deasphalting solvent can be substantially free of propane, butane,and/or other C₃-C₄ hydrocarbons (less than 1 wt %). In aspects where thedeasphalting solvent corresponds to a C₃₊ deasphalting solvent, the C₃₊deasphalting solvent can include less than 10 wt % ethane and/or otherC₂ hydrocarbons, or less than 5 wt %, or the C₃₊ deasphalting solventcan be substantially free of ethane and/or other C₂ hydrocarbons (lessthan 1 wt %).

Deasphalting of heavy hydrocarbons, such as vacuum resids, is known inthe art and practiced commercially. A deasphalting process typicallycorresponds to contacting a heavy hydrocarbon with an alkane solvent(propane, butane, pentane, hexane, heptane etc and their isomers),either in pure form or as mixtures, to produce two types of productstreams. One type of product stream can be a deasphalted oil extractedby the alkane, which is further separated to produce deasphalted oilstream. A second type of product stream can be a residual portion of thefeed not soluble in the solvent, often referred to as rock or asphaltenefraction. The deasphalted oil fraction can be further processed intomake fuels or lubricants. The rock fraction can be further used as blendcomponent to produce asphalt, fuel oil, and/or other products. The rockfraction can also be used as feed to gasification processes such aspartial oxidation, fluid bed combustion or coking processes. The rockcan be delivered to these processes as a liquid (with or withoutadditional components) or solid (either as pellets or lumps).

During solvent deasphalting, a resid boiling range feed (optionally alsoincluding a portion of a vacuum gas oil feed) can be mixed with asolvent. Portions of the feed that are soluble in the solvent are thenextracted, leaving behind a residue with little or no solubility in thesolvent. The portion of the deasphalted feedstock that is extracted withthe solvent is often referred to as deasphalted oil. Typical solventdeasphalting conditions include mixing a feedstock fraction with asolvent in a weight ratio of from about 1:2 to about 1:10, such as about1:8 or less. Typical solvent deasphalting temperatures range from 40° C.to 200° C., or 40° C. to 150° C., depending on the nature of the feedand the solvent. The pressure during solvent deasphalting can be fromabout 50 psig (345 kPag) to about 500 psig (3447 kPag).

It is noted that the above solvent deasphalting conditions represent ageneral range, and the conditions will vary depending on the feed. Forexample, under typical deasphalting conditions, increasing thetemperature can tend to reduce the yield while increasing the quality ofthe resulting deasphalted oil. Under typical deasphalting conditions,increasing the molecular weight of the solvent can tend to increase theyield while reducing the quality of the resulting deasphalted oil, asadditional compounds within a resid fraction may be soluble in a solventcomposed of higher molecular weight hydrocarbons. Under typicaldeasphalting conditions, increasing the amount of solvent can tend toincrease the yield of the resulting deasphalted oil. As understood bythose of skill in the art, the conditions for a particular feed can beselected based on the resulting yield of deasphalted oil from solventdeasphalting. In aspects where a C₃ deasphalting solvent is used, theyield from solvent deasphalting can be 40 wt % or less. In some aspects,C₄ deasphalting can be performed with a yield of deasphalted oil of 50wt % or less, or 40 wt % or less. In various aspects, the yield ofdeasphalted oil from solvent deasphalting with a C₄₊ solvent can be atleast 50 wt % relative to the weight of the feed to deasphalting, or atleast 55 wt %, or at least 60 wt % or at least 65 wt %, or at least 70wt %. In aspects where the feed to deasphalting includes a vacuum gasoil portion, the yield from solvent deasphalting can be characterizedbased on a yield by weight of a 950° F.+(510° C.) portion of thedeasphalted oil relative to the weight of a 510° C.+ portion of thefeed. In such aspects where a C₄₊ solvent is used, the yield of 510° C.+deasphalted oil from solvent deasphalting can be at least 40 wt %relative to the weight of the 510° C.+ portion of the feed todeasphalting, or at least 50 wt %, or at least 55 wt %, or at least 60wt % or at least 65 wt %, or at least 70 wt %. In such aspects where aC⁴⁻ solvent is used, the yield of 510° C.+ deasphalted oil from solventdeasphalting can be 50 wt % or less relative to the weight of the 510°C.+ portion of the feed to deasphalting, or 40 wt % or less, or 35 wt %or less.

Multimetallic Catalyst and Forming Multimetallic Catalyst from aPrecursor Including Organic Components

As used herein, the term “bulk”, when describing a mixed metal oxidecatalyst composition, indicates that the catalyst composition isself-supporting in that it does not require a carrier or support. It iswell understood that bulk catalysts may have some minor amount ofcarrier or support material in their compositions (e.g., about 20 wt %or less, about 15 wt % or less, about 10 wt % or less, about 5 wt % orless, or substantially no carrier or support, based on the total weightof the catalyst composition); for instance, bulk hydroprocessingcatalysts may contain a minor amount of a binder, e.g., to improve thephysical and/or thermal properties of the catalyst. In contrast,heterogeneous or supported catalyst systems typically comprise a carrieror support onto which one or more catalytically active materials aredeposited, often using an impregnation or coating technique.Nevertheless, heterogeneous catalyst systems without a carrier orsupport (or with a minor amount of carrier or support) are generallyreferred to as bulk catalysts and are frequently formed byco-precipitation or solid-solid reactions in slurries.

In various aspects, the methods described herein can include use of acatalyst formed from a catalyst precursor composition comprising atleast one metal from Group 6 of the Periodic Table of the Elements, atleast one metal from Groups 8-10 of the Periodic Table of the Elements.The catalyst precursor compositions can either further include areaction product, or the catalyst precursor can be treated withcompounds used to form such a reaction product in situ.

The reaction product can be formed in various manners. In some aspects,the reaction product can be formed from (i) a first organic compoundcontaining at least one amine group and at least 10 carbons or (ii) asecond organic compound containing at least one carboxylic acid groupand at least 10 carbons, but not both (i) and (ii), wherein the reactionproduct contains additional unsaturated carbon atoms, relative to (i)the first organic compound or (ii) the second organic compound, whereinthe metals of the catalyst precursor composition are arranged in acrystal lattice, and wherein the reaction product is not located withinthe crystal lattice. Additionally or alternately, in some aspects thereaction product can be formed from (i) a first organic compoundcontaining at least one amine group, and (ii) a second organic compoundseparate from said first organic compound and containing at least onecarboxylic acid group. More broadly, this type of aspect relates to useof a catalyst formed from a catalyst precursor composition comprising atleast one metal from Group 6 of the Periodic Table of the Elements, atleast one metal from Groups 8-10 of the Periodic Table of the Elements,and a condensation reaction product formed from (i) a first organiccompound containing at least one first functional group, and (ii) asecond organic compound separate from said first organic compound andcontaining at least one second functional group, wherein said firstfunctional group and said second functional group are capable ofundergoing a condensation reaction and/or a (decomposition) reactioncausing an additional unsaturation to form an associated product. Thoughthe description above and herein often refers specifically to thecondensation reaction product being an amide, it should be understoodthat any in situ condensation reaction product formed can be substitutedfor the amide described herein. For example, if the first functionalgroup is a hydroxyl group and the second functional group is acarboxylic acid or an acid chloride or an organic ester capable ofundergoing transesterification with the hydroxyl group, then the in situcondensation reaction product formed would be an ester. When thisreaction product is an amide, the presence of the reaction product inany intermediate or final composition can be determined by methods wellknown in the art, e.g., by infrared spectroscopy (FTIR) techniques. Whenthis reaction product contains additional unsaturation(s) not present inthe first and second organic compounds, e.g., from at least partialdecomposition/dehydrogenation at conditions including elevatedtemperatures, the presence of the additional unsaturation(s) in anyintermediate or final composition can be determined by methods wellknown in the art, e.g., by FTIR and/or nuclear magnetic resonance (¹³CNMR) techniques. This catalyst precursor composition can be a bulk metalcatalyst precursor composition or a heterogeneous (supported) metalcatalyst precursor composition.

This catalyst precursor composition can be a bulk metal catalystprecursor composition or a supported metal catalyst precursorcomposition. When it is a bulk mixed metal catalyst precursorcomposition, the reaction product can be obtained by heating thecomposition (though specifically the amine-containing compound or thecarboxylic acid-containing compound) to a temperature from about 195° C.to about 260° C. for a time sufficient for the first or second organiccompounds to react to form additional in situ unsaturated carbon atomsand/or become more oxidized than the first or second organic compounds,but not for so long that more than 50% by weight of the first or secondorganic compound is volatilized, thereby forming a catalyst precursorcomposition that contains in situ formed unsaturated carbon atoms and/orthat is further oxidized.

A bulk mixed metal hydroprocessing catalyst composition can be producedfrom this bulk mixed metal catalyst precursor composition by sulfidingit under sufficient sulfiding conditions, which sulfiding should beginin the presence of the in situ additionally unsaturated reaction product(which may result from at least partial decomposition, e.g., viaoxidative dehydrogenation in the presence of oxygen and/or vianon-oxidative dehydrogenation in the absence of an appropriateconcentration of oxygen, of typically-unfunctionalized organic portionsof the first or second organic compounds, e.g., of an aliphatic portionof an organic compound and/or through conjugation/aromatization ofunsaturations expanding upon an unsaturated portion of an organiccompound).

When the catalyst precursor is a bulk mixed metal catalyst precursorcomposition that includes an ex situ or in situ formed amide, thethermal treatment of the amide-impregnated metal oxide component iscarried out by heating the impregnated composition to a temperature andfor a time which does not result in gross decomposition of the amide,although additional unsaturation may arise from partial in situdecomposition; the temperature is typically from about 195° C. to about250° C. (or optionally about 195° C. to about 260° C.), but highertemperatures, e.g. in the range of 250 to 280° C., can be used in orderto abbreviate the duration of the heating although due care is requiredto avoid the gross decomposition of the pre-formed amide, as discussedfurther below. The bulk mixed metal hydroprocessing catalyst can beproduced from this precursor by sulfiding it with the sulfiding takingplace with the amide present on the metal oxide component (i.e., whenthe thermally treated amide, is substantially present and/or preferablynot significantly decomposed by the beginning of the sulfiding step).Additional unsaturation may be present in the organic component of thecatalyst precursor resulting from a variety of mechanisms includingpartial decomposition, (e.g., via oxidative dehydrogenation in thepresence of oxygen and/or via non-oxidative dehydrogenation in theabsence of an appropriate concentration of oxygen), oftypically-unfunctionalized organic portions of the amide and/or throughconjugation/aromatization of unsaturations expanding upon an unsaturatedportion the amide. The treated organic component may also containadditional oxygen in addition to the unsaturation when the treatment iscarried out in an oxidizing atmosphere.

Catalyst precursor compositions and hydroprocessing catalystcompositions useful in various aspects of the present invention canadvantageously comprise (or can have metal components that consistessentially of) at least one metal from Group 6 of the Periodic Table ofElements and at least one metal from Groups 8-10 of the Periodic Tableof Elements, and optionally at least one metal from Group 5 of thePeriodic Table of Elements. Generally, these metals are present in theirsubstantially fully oxidized form, which can typically take the form ofsimple metal oxides, but which may be present in a variety of otheroxide forms, e.g., such as hydroxides, oxyhydroxides, oxycarbonates,carbonates, oxynitrates, oxysulfates, or the like, or some combinationthereof. In one preferred embodiment, the Group 6 metal(s) can be Moand/or W, and the Group 8-10 metal(s) can be Co and/or Ni. Generally,the atomic ratio of the Group 6 metal(s) to the metal(s) of Groups 8-10can be from about 2:1 to about 1:3, for example from about 5:4 to about1:2, or from about 20:19 to about 3:4. When the composition furthercomprises at least one metal from Group 5, that at least one metal canbe V and/or Nb. When present, the amount of Group 5 metal(s) can be suchthat the atomic ratio of the Group 6 metal(s) to the Group 5 metal(s)can be from about 99:1 to about 1:1, for example from about 99:1 toabout 5:1, from about 99:1 to about 10:1, or from about 99:1 to about20:1. Additionally or alternately, when Group 5 metal(s) is(are)present, the atomic ratio of the sum of the Group 5 metal(s) plus theGroup (6) metal(s) compared to the metal(s) of Groups 8-10 can be fromabout 2:1 to about 1:3, for example from about 5:4 to about 1:2, or fromabout 20:19 to about 3:4.

The metals in the catalyst precursor compositions and in thehydroprocessing catalyst compositions according to the invention can bepresent in any suitable form prior to sulfiding, but can often beprovided as metal oxides. When provided as bulk mixed metal oxides, suchbulk oxide components of the catalyst precursor compositions and of thehydroprocessing catalyst compositions according to the invention can beprepared by any suitable method known in the art, but can generally beproduced by forming a slurry, typically an aqueous slurry, comprising(1) (a) an oxyanion of the Group 6 metal(s), such as a tungstate and/ora molybdate, or (b) an insoluble (oxide, acid) form of the Group 6metal(s), such as tungstic acid and/or molybdenum trioxide, (2) a saltof the Group 8-10 metal(s), such as nickel carbonate, and optionally,when present, (3) (a) a salt or oxyanion of a Group 5 metal, such as avanadate and/or a niobate, or (b) insoluble (oxide, acid) form of aGroup 5 metal, such as niobic acid and/or diniobium pentoxide. Theslurry can be heated to a suitable temperature, such as from about 60°C. to about 150° C., at a suitable pressure, e.g., at atmospheric orautogenous pressure, for an appropriate time, e.g., about 4 hours toabout 24 hours.

Non-limiting examples of suitable mixed metal oxide compositions caninclude, but are not limited to, nickel-tungsten oxides, cobalt-tungstenoxides, nickel-molybdenum oxides, cobalt-molybdenum oxides,nickel-molybdenum-tungsten oxides, cobalt-molybdenum-tungsten oxides,cobalt-nickel-tungsten oxides, cobalt-nickel-molybdenum oxides,cobalt-nickel-tungsten-molybdenum oxides, nickel-tungsten-niobiumoxides, nickel-tungsten-vanadium oxides, cobalt-tungsten-vanadiumoxides, cobalt-tungsten-niobium oxides, nickel-molybdenum-niobiumoxides, nickel-molybdenum-vanadium oxides,nickel-molybdenum-tungsten-niobium oxides,nickel-molybdenum-tungsten-vanadium oxides, and the like, andcombinations thereof.

Suitable mixed metal oxide compositions can advantageously exhibit aspecific surface area (as measured via the nitrogen BET method using aQuantachrome Autosorb™ apparatus) of about 20 m²/g to about 500 m²/g, orabout 30 m²/g to about 300 m²/g, or about 50 m²/g to about 150 m²/g.

In some aspects, after separating and drying the mixed metal oxide(slurry) composition, it can be treated, generally by impregnation withthe reaction product and/or the reagents that are suitable for formingthe reaction product.

In some aspects, the first and/or second organic compound can compriseat least 10 carbon atoms, for example can comprise from 10 to 20 carbonatoms or can comprise a primary monoamine having from 10 to 30 carbonatoms. Additionally or alternately, the second organic compound cancomprise at least 10 carbon atoms, for example can comprise from 10 to20 carbon atoms or can comprise only one carboxylic acid group and canhave from 10 to 30 carbon atoms. Further additionally or alternately,the total number of carbon atoms comprised among both the first andsecond organic compounds can be at least 15 carbon atoms, for example atleast 20 carbon atoms, at least 25 carbon atoms, at least 30 carbonatoms, or at least 35 carbon atoms, such as optionally up to 70 carbonatoms, or optionally up to 100 carbon atoms.

Representative examples of organic compounds containing amine groups caninclude, but are not limited to, primary and/or secondary, linear,branched, and/or cyclic amines, such as triacontanylamine,octacosanylamine, hexacosanylamine, tetracosanylamine, docosanylamine,erucylamine, eicosanylamine, octadecylamine, oleylamine, linoleylamine,hexadecylamine, sapienylamine, palmitoleylamine, tetradecylamine,myristoleylamine, dodecylamine, decylamine, nonylamine, cyclooctylamine,octylamine, cycloheptylamine, heptylamine, cyclohexylamine,n-hexylamine, isopentylamine, n-pentylamine, t-butylamine, n-butylamine,isopropylamine, n-propylamine, adamantanamine, adamantanemethylamine,pyrrolidine, piperidine, piperazine, imidazole, pyrazole, pyrrole,pyrrolidine, pyrroline, indazole, indole, carbazole, norbornylamine,aniline, pyridylamine, benzylamine, aminotoluene, alanine, arginine,aspartic acid, glutamic acid, glutamine, glycine, histidine, isoleucine,leucine, lysine, phenylalanine, serine, threonine, valine,1-amino-2-propanol, 2-amino-1-propanol, diaminoeicosane,diaminooctadecane, diaminohexadecane, diaminotetradecane,diaminododecane, diaminodecane, 1,2-diaminocyclohexane,1,3-diaminocyclohexane, 1,4-diaminocyclohexane, ethylenediamine,ethanolamine, p-phenylenediamine, o-phenylenediamine,m-phenylenediamine, 1,2-propylenediamine, 1,3-propylenediamine,1,4-diaminobutane, 1,3diamino-2-propanol, and the like, and combinationsthereof. In an embodiment, the molar ratio of the Group 6 metal(s) inthe composition to the first organic compound during treatment can befrom about 1:1 to about 20:1.

Additionally or alternately, in some aspects the amine portion of thefirst organic compound can be a part of a larger functional group inthat compound, so long as the amine portion (notably the amine nitrogenand the constituents attached thereto) retains its operability as aLewis base. For instance, the first organic compound can comprise aurea, which functional group comprises an amine portion attached to thecarbonyl portion of an amide group. In such an instance, the urea can beconsidered functionally as an “amine-containing” functional group forthe purposes of the present invention herein, except in situations wheresuch inclusion is specifically contradicted. Aside from ureas, otherexamples of such amine-containing functional groups that may be suitablefor satisfying the at least one amine group in the first organiccompound can generally include, but are not limited to, hydrazides,sulfonamides, and the like, and combinations thereof.

The amine functional group from the first organic compound can includeprimary or secondary amines, as mentioned above, but generally does notinclude tertiary or quaternary amines, as tertiary and quaternary aminestend not to be able to form amides. Furthermore, the first organiccompound can contain other functional groups besides amines, whether ornot they are capable of participating in forming an amide or othercondensation reaction product with one or more of the functional groupsfrom second organic compound. For instance, the first organic compoundcan comprise an amino acid, which possesses an amine functional groupand a carboxylic acid functional group simultaneously. In such aninstance, the amino acid would qualify as only one of the organiccompounds, and not both; thus, in such an instance, either an additionalamine-containing (first) organic compound would need to be present (inthe circumstance where the amino acid would be considered the secondorganic compound) or an additional carboxylic acid-containing (second)organic compound would need to be present (in the circumstance where theamino acid would be considered the first organic compound). Aside fromcarboxylic acids, other examples of such secondary functional groups inamine-containing organic compounds can generally include, but are notlimited to, hydroxyls, aldehydes, anhydrides, ethers, esters, imines,imides, ketones, thiols (mercaptans), thioesters, and the like, andcombinations thereof.

Representative examples of organic compounds containing carboxylic acidscan include, but are not limited to, primary and/or secondary, linear,branched, and/or cyclic amines, such as triacontanoic acid, octacosanoicacid, hexacosanoic acid, tetracosanoic acid, docosanoic acid, erucicacid, docosahexanoic acid, eicosanoic acid, eicosapentanoic acid,arachidonic acid, octadecanoic acid, oleic acid, elaidic acid,stearidonic acid, linoleic acid, alpha-linolenic acid, hexadecanoicacid, sapienic acid, palmitoleic acid, tetradecanoic acid, myristoleicacid, dodecanoic acid, decanoic acid, nonanoic acid, cyclooctanoic acid,octanoic acid, cycloheptanoic acid, heptanoic acid, cyclohexanoic acid,hexanoic acid, adamantanecarboxylic acid, norbornaneacetic acid, benzoicacid, salicylic acid, acetylsalicylic acid, citric acid, maleic acid,malonic acid, glutaric acid, lactic acid, oxalic acid, tartaric acid,cinnamic acid, vanillic acid, succinic acid, adipic acid, phthalic acid,isophthalic acid, terephthalic acid, ethylenediaminetetracarboxylicacids (such as EDTA), fumaric acid, alanine, arginine, aspartic acid,glutamic acid, glutamine, glycine, histidine, isoleucine, leucine,lysine, phenylalanine, serine, threonine, valine,1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,1,4-cyclohexanedicarboxylic acid, and the like, and combinationsthereof. In an embodiment, the molar ratio of the Group 6 metal(s) inthe composition to the second organic compound during treatment can befrom about 3:1 to about 20:1.

In some aspects, the second organic compound can optionally containother functional groups besides carboxylic acids. For instance, thesecond organic compound can comprise an aminoacid, which possesses acarboxylic acid functional group and an amine functional groupsimultaneously. Aside from amines, other examples of such secondaryfunctional groups in carboxylic acid-containing organic compounds cangenerally include, but are not limited to, hydroxyls, aldehydes,anhydrides, ethers, esters, imines, imides, ketones, thiols(mercaptans), thioesters, and the like, and combinations thereof. Insome embodiments, the second organic compound can contain no additionalamine or alcohol functional groups in addition to the carboxylic acidfunctional group(s).

Additionally or alternately, the reactive portion of the second organiccompound can be a part of a larger functional group in that compoundand/or can be a derivative of a carboxylic acid that behaves similarlyenough to a carboxylic acid, such that the reactive portion and/orderivative retains its operability as a Lewis acid. One example of acarboxylic acid derivative can include an alkyl carboxylate ester, wherethe alkyl group does not substantially hinder (over a reasonable timescale) the Lewis acid functionality of the carboxylate portion of thefunctional group.

For aspects involving formation of a condensation product (includingaspects involving ex situ formation of an amide), while there is not astrict limit on the ratio between the first organic compound and thesecond organic compound, because the goal of the addition of the firstand second organic compounds is to attain a condensation reactionproduct, it may be desirable to have a ratio of the reactive functionalgroups within the first and second organic compounds, respectively, fromabout 1:4 to about 4:1, for example from about 1:3 to about 3:1 or fromabout 1:2 to about 2:1. In some optional aspects, tt has been observedthat catalysts made with amides from equimolar quantities of the amineand carboxylic acid reactants compounds show performance improvements inhydroprocessing certain feeds and for this reason, amides made with anequimolar ratio are preferred.

In certain aspects, the organic compound(s)/additive(s) and/or thereaction product(s) are not located/incorporated within the crystallattice of the mixed metal oxide precursor composition, e.g., insteadbeing located on the surface and/or within the pore volume of theprecursor composition and/or being associated with (bound to) one ormore metals or oxides of metals in a manner that does not significantlyaffect the crystalline lattice of the mixed metal oxide precursorcomposition, as observed through XRD and/or other crystallographicspectra. It is noted that, in these certain embodiments, a sulfidedversion of the mixed metal oxide precursor composition can still haveits sulfided form affected by the organic compound(s)/additive(s) and/orthe reaction product(s), even though the oxide lattice is notsignificantly affected.

Practically, the treating step (a) above can comprise one (or more) ofthree methods: (1) first treating the catalyst precursor compositionwith the first organic compound and second with the second organiccompound; (2) first treating the catalyst precursor composition with thesecond organic compound and second with the first organic compound;and/or (3) treating the catalyst precursor composition simultaneouslywith the first organic compound and with the second organic compound.

In certain advantageous embodiments, the heating step (b) above can beconducted for a sufficiently long time so as to form an amide, but notfor so long that the amide so formed substantially decomposes.Additionally or alternately, the heating step (b) above can be conductedfor a sufficiently long time so as to form additional unsaturation(s),which may result from at least partial decomposition (e.g., oxidativeand/or non-oxidative dehydrogenation and/or aromatization) of some(typically-unfunctionalized organic) portions of the organic compounds,but generally not for so long that the at least partial decomposition(i) substantially decomposes any condensation product, such as amide,and/or (ii) volatilizes more than 50% by weight of the combined firstand second organic compounds.

It is contemplated that the specific lower and upper temperature limitsbased on the above considerations can be highly dependent upon a varietyof factors that can include, but are not limited to, the atmosphereunder which the heating is conducted, the chemical and/or physicalproperties of the first organic compound, the second organic compound,the reaction product, and/or any reaction byproduct, or a combinationthereof. In one embodiment, the heating temperature can be at leastabout 120° C., for example about 150° C. or more, or about 210° C. ormore, or about 250° C. or more. Additionally or alternately, the heatingtemperature can be not greater than about 400° C., for example notgreater than about 350° C., not greater than about 300° C., not greaterthan about 250° C., or not greater than about 200° C.

In one embodiment, the heating can be conducted in a low- ornon-oxidizing atmosphere (and conveniently in an inert atmosphere, suchas nitrogen). In an alternate embodiment, the heating can be conductedin a moderately- or highly-oxidizing environment. In another alternateembodiment, the heating can include a multi-step process in which one ormore heating steps can be conducted in the low- or non-oxidizingatmosphere, in which one or more heating steps can be conducted in themoderately- or highly-oxidizing environment, or both. Of course, theperiod of time for the heating in the environment can be tailored to thefirst or second organic compound, but can typically extend from about 5minutes to about 168 hours, for example from about 10 minutes to about96 hours, from about 20 minutes to about 48 hours, from about 30 minutesto about 24 hours, or from about 1 hour to about 4 hours.

Additionally or alternately, in aspects where an ex situ formed amide isused, the amide can be formed prior to impregnation into the metal oxidecomponent of the catalyst precursor by reaction of the amine componentand the carboxylic acid component. Reaction typically takes placereadily at mildly elevated temperatures up to about 200° C. withliberation of water as a by-product of the reaction at temperaturesabove 100° C. and usually above 150° C. The reactants can usually beheated together to form a melt in which the reaction takes place and themelt impregnated directly into the metal oxide component which ispreferably pre-heated to the same temperature as the melt in order toassist penetration into the structure of the metal oxide component. Thereaction can also be carried out in the presence of a solvent if desiredand the resulting solution used for the impregnation step. In certainembodiments, the amide and its heat treated derivative may not belocated/incorporated within the crystal lattice of the mixed metal oxideprecursor, e.g., may instead be located on the surface and/or within thepore volume of the precursor and/or be associated with (bound to) one ormore metals or oxides of metals in a manner that does not significantlyaffect the crystalline lattice of the mixed metal oxide precursorcomposition, as observed through XRD and/or other crystallographicspectra. A sulfided version of the mixed metal oxide precursorcomposition can still have its sulfided form affected by the organiccompound(s)/additive(s) and/or the reaction product(s), even though theoxide lattice is not significantly affected.

In an embodiment, the organically treated catalyst precursor compositionand/or the catalyst precursor composition containing the reactionproduct can contain from about 4 wt % to about 20 wt %, for example fromabout 5 wt % to about 15 wt %, carbon resulting from the first andsecond organic compounds and/or from the condensation product, asapplicable, based on the total weight of the relevant composition.

Additionally or alternately, as a result of the heating step, thereaction product from the organically treated catalyst precursor canexhibit a content of unsaturated carbon atoms (which includes aromaticcarbon atoms), as measured according to peak area comparisons using ¹³CNMR techniques, of at least 29%, for example at least about 30%, atleast about 31%, at least about 32%, or at least about 33%. Furtheradditionally or alternately, the reaction product from the organicallytreated catalyst precursor can optionally exhibit a content ofunsaturated carbon atoms (which includes aromatic carbon atoms), asmeasured according to peak area comparisons using ¹³C NMR techniques, ofup to about 70%, for example up to about 65%, up to about 60%, up toabout 55%, up to about 50%, up to about 45%, up to about 40%, or up toabout 35%. Still further additionally or alternately, as a result of theheating step, the reaction product from the organically treated catalystprecursor can exhibit an increase in content of unsaturated carbon atoms(which includes aromatic carbon atoms), as measured according to peakarea comparisons using ¹³C NMR techniques, of at least about 17%, forexample at least about 18%, at least about 19%, at least about 20%, orat least about 21% (e.g., in an embodiment where the first organiccompound is oleylamine and the second organic compound is oleic acid,such that the combined unsaturation level of the unreacted compounds isabout 11.1% of carbon atoms, a .about.17% increase in unsaturatedcarbons upon heating corresponds to about 28.1% content of unsaturatedcarbon atoms in the reaction product). Yet further additionally oralternately, the reaction product from the organically treated catalystprecursor can optionally exhibit an increase in content of unsaturatedcarbon atoms (which includes aromatic carbon atoms), as measuredaccording to peak area comparisons using ¹³C NMR techniques, of up toabout 60%, for example up to about 55%, up to about 50%, up to about45%, up to about 40%, up to about 35%, up to about 30%, or up to about25%.

Again further additionally or alternately, as a result of the heatingstep, the reaction product from the organically treated catalystprecursor can exhibit a ratio of unsaturated carbon atoms to aromaticcarbon atoms, as measured according to peak area ratios using infraredspectroscopic techniques of a deconvoluted peak centered from about 1700cm⁻¹ to about 1730 cm⁻¹ (e.g., at about 1715 cm⁻¹), compared to adeconvoluted peak centered from about 1380 cm⁻¹ to about 1450 cm⁻¹(e.g., from about 1395 cm⁻¹ to about 1415 cm⁻¹), of at least 0.9, forexample at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least1.4, at least 1.5, at least 1.7, at least 2.0, at least 2.2, at least2.5, at least 2.7, or at least 3.0. Again still further additionally oralternately, the reaction product from the organically treated catalystprecursor can exhibit a ratio of unsaturated carbon atoms to aromaticcarbon atoms, as measured according to peak area ratios using infraredspectroscopic techniques of a deconvoluted peak centered from about 1700cm⁻¹ to about 1730 cm⁻¹ (e.g., at about 1715 cm⁻¹), compared to adeconvoluted peak centered from about 1380 cm⁻¹ to about 1450 cm⁻¹(e.g., from about 1395 cm⁻¹ to about 1415 cm⁻¹), of up to 15, forexample up to 10, up to 8.0, up to 7.0, up to 6.0, up to 5.0, up to 4.5,up to 4.0, up to 3.5, or up to 3.0.

A (sulfided) hydroprocessing catalyst composition can then be producedby sulfiding the catalyst precursor composition containing the reactionproduct. Sulfiding is generally carried out by contacting the catalystprecursor composition containing the reaction product with asulfur-containing compound (e.g., elemental sulfur, hydrogen sulfide,polysulfides, or the like, or a combination thereof, which may originatefrom a fossil/mineral oil stream, from a biocomponent-based oil stream,from a combination thereof, or from a sulfur-containing stream separatefrom the aforementioned oil stream(s)) at a temperature and for a timesufficient to substantially sulfide the composition and/or sufficient torender the sulfided composition active as a hydroprocessing catalyst.For instance, the sulfidation can be carried out at a temperature fromabout 300° C. to about 400° C., e.g., from about 310° C. to about 350°C., for a period of time from about 30 minutes to about 96 hours, e.g.,from about 1 hour to about 48 hours or from about 4 hours to about 24hours. The sulfiding can generally be conducted before or aftercombining the metal (oxide) containing composition with a binder, ifdesired, and before or after forming the composition into a shapedcatalyst. The sulfiding can additionally or alternately be conducted insitu in a hydroprocessing reactor. Obviously, to the extent that areaction product of the first or second organic compounds containsadditional unsaturations formed in situ, it would generally be desirablefor the sulfidation (and/or any catalyst treatment after the organictreatment) to significantly maintain the in situ formed additionalunsaturations of said reaction product.

The sulfided catalyst composition can exhibit a layered structurecomprising a plurality of stacked YS₂ layers, where Y is the Group 6metal(s), such that the average number of stacks (typically for bulkorganically treated catalysts) can be from about 1.5 to about 3.5, forexample from about 1.5 to about 3.0, from about 2.0 to about 3.3, fromabout 2.0 to about 3.0, or from about 2.1 to about 2.8. For instance,the treatment of the metal (oxide) containing precursor compositionaccording to the invention can afford a decrease in the average numberof stacks of the treated precursor of at least about 0.8, for example atleast about 1.0, at least about 1.2, at least about 1.3, at least about1.4, or at least about 1.5, as compared to an untreated metal (oxide)containing precursor composition. As such, the number of stacks can beconsiderably less than that obtained with an equivalent sulfided mixedmetal (oxide) containing precursor composition produced without thefirst or second organic compound treatment. The reduction in the averagenumber of stacks can be evidenced, e.g., via X-ray diffraction spectraof relevant sulfided compositions, in which the (002) peak appearssignificantly broader (as determined by the same width at thehalf-height of the peak) than the corresponding peak in the spectrum ofthe sulfided mixed metal (oxide) containing precursor compositionproduced without the organic treatment (and/or, in certain cases, withonly a single organic compound treatment using an organic compoundhaving less than 10 carbon atoms) according to the present invention.Additionally or alternately to X-ray diffraction, transmission electronmicroscopy (TEM) can be used to obtain micrographs of relevant sulfidedcompositions, including multiple microcrystals, within which micrographimages the multiple microcrystals can be visually analyzed for thenumber of stacks in each, which can then be averaged over the micrographvisual field to obtain an average number of stacks that can evidence areduction in average number of stacks compared to a sulfided mixed metal(oxide) containing precursor composition produced without the organictreatment (and/or, in certain cases, with only a single organic compoundtreatment) according to the present invention.

Multimetallic Catalyst and Forming Multimetallic Catalyst from Reactantsat Least Partially in the Solid State

In various aspects, another option for a bulk multimetallic catalyst isto use a bulk multimetallic catalyst comprised of at least one GroupVIII non-noble metal and at least two Group VIB metals and wherein theratio of Group VIB metal to Group VIII non-noble metal is from about10:1 to about 1:10. It is preferred that the catalyst be a bulktrimetallic catalyst comprised of one Group VIII non-noble metal,preferably Ni or Co and the two Group VIB metals Mo and W. It ispreferred that the ratio of Mo to W be about 9:1 to about 1:9.

The preferred bulk trimetallic catalyst compositions used in thepractice of the present invention is represented by the formula:

(X)_(b)(Mo)_(c)(W)_(d)O_(x)

wherein X is one or more Group VIII non-noble metal, the molar ratio ofb:(c+d) is 0.5/1 to 3/1, preferably 0.75/1 to 1.5/1, more preferably0.75/1 to 1.25/1; The molar ratio of c:d is preferably >0.01/1, morepreferably >0.1/1, still more preferably 1/10 to 10/1, still morepreferably 1/3 to 3/1, most preferably substantially equimolar amountsof Mo and W, e.g., 2/3 to 3/2; and z=[2b+6(c+d)]/2.

The essentially amorphous material has a unique X-ray diffractionpattern showing crystalline peaks at d=2.53 Angstroms and d=1.70Angstroms.

The mixed metal oxide is readily produced by the decomposition of aprecursor having the formula:

(NH₄)_(a)(X)_(b)(Mo)_(c)(W)_(d)O_(x)

wherein the molar ratio of a:b is ≤1.0/1, preferably 0-1; and b, c, andd, are as defined above, and z=[a+2b+6(c+d)]/2. The precursor hassimilar peaks at d=2.53 and 1.70 Angstroms.

Decomposition of the precursor may be effected at elevated temperatures,e.g., temperatures of at least about 300° C., preferably about 300-450°C., in a suitable atmosphere, e.g., inerts such as nitrogen, argon, orsteam, until decomposition is substantially complete, i.e., the ammoniumis substantially completely driven off. Substantially completedecomposition can be readily established by thermogravimetric analysis(TGA), i.e., flattening of the weight change curve.

The catalyst compositions used in the practice of the present inventioncan be prepared by any suitable means. One such means is a methodwherein not all of the metals are in solution. Generally, the contactingof the metal components in the presence of the protic liquid comprisesmixing the metal component and subsequently reacting the resultingmixture. It is essential to the solid route that at least one metalcomponents is added at least partly in the solid state during the mixingstep and that the metal of at least one of the metal components whichhave been added at least partly in the solid state, remains at leastpartly in the solid state during the mixing and reaction step. “Metal”in this context does not mean the metal in its metallic form but presentin a metal compound, such as the metal component as initially applied oras present in the bulk catalyst composition.

Generally, during the mixing step either at least one metal component isadded at least partly in the solid state and at least one metalcomponent is added in the solute state, or all metal components areadded at least partly in the solid state, wherein at least one of themetals of the metal components which are added at least partly in thesolid state remains at least partly in the solid state during the entireprocess of the solid route. That a metal component is added “in thesolute state” means that the whole amount of this metal component isadded as a solution of this metal component in the protic liquid. That ametal component is added “at least partly in the solid state” means thatat least part of the metal component is added as solid metal componentand, optionally, another part of the metal component is added as asolution of this metal component in the protic liquid. A typical exampleis a suspension of a metal component in a protic liquid in which themetal is at least partly present as a solid, and optionally partlydissolved in the protic liquid.

To obtain a bulk catalyst composition with high catalytic activity, itis therefore preferred that the metal components, which are at leastpartly in the solid state during contacting, are porous metalcomponents. It is desired that the total pore volume and pore sizedistribution of these metal components is approximately the same asthose of conventional hydrotreating catalysts. Conventionalhydrotreating catalysts generally have a pore volume of 0.05-5 ml/g,preferably of 0.1-4 ml/g, more preferably of 0.1-3 ml/g and mostpreferably of 0.1-2 ml/g determined by nitrogen adsorption. Pores with adiameter smaller than 1 nm are generally not present in conventionalhydrotreating catalysts. Further, conventional hydrotreating catalystshave generally a surface area of at least 10 m²/g and more preferably ofat least 50 m²/g and most preferably of at least 100 m²/g, determinedvia the B.E.T. method. For instance, nickel carbonate can be chosenwhich has a total pore volume of 0.19-0.39 ml/g and preferably of0.24-0.35 ml/g determined by nitrogen adsorption and a surface area of150-400 m²/g and more preferably of 200-370 m²/g determined by theB.E.T. method. Furthermore these metal components should have a medianparticle diameter of at least 50 nm, more preferably at least 100 nm,and preferably not more than 5000 μm and more preferably not more than3000 μm. Even more preferably, the median particle diameter lies in therange of 0.1-50 μm and most preferably in the range of 0.5-50 μm. Forinstance, by choosing a metal component which is added at least partlyin the solid state and which has a large median particle diameter, theother metal components will only react with the outer layer of the largemetal component particle. In this case, so-called “core-shell”structured bulk catalyst particles are obtained.

An appropriate morphology and texture of the metal component can eitherbe achieved by applying suitable preformed metal components or bypreparing these metal components by the above-described precipitationunder such conditions that a suitable morphology and texture isobtained. A proper selection of appropriate precipitation conditions canbe made by routine experimentation.

As has been set out above, to retain the morphology and texture of themetal components which are added at least partly in the solid state, itis essential that the metal of the metal component at least partlyremains in the solid state during the whole process of this solid route.It is noted again that it is essential that in no case should the amountof solid metals during the process of the solid route becomes zero. Thepresence of solid metal comprising particles can easily be detected byvisual inspection at least if the diameter of the solid particles inwhich the metals are comprised is larger than the wavelength of visiblelight. Of course, methods such as quasi-elastic light scattering (QELS)or near forward scattering which are known to the skilled person canalso be used to ensure that in no point in time of the process of thesolid route, all metals are in the solute state.

The protic liquid to be applied in the solid or solution route of thisinvention for preparing catalyst can be any protic liquid. Examplesinclude water, carboxylic acids, and alcohols such as methanol orethanol. Preferably, a liquid comprising water such as mixtures of analcohol and water and more preferably water is used as protic liquid inthis solid route. Also different protic liquids can be appliedsimultaneously in the solid route. For instance, it is possible to add asuspension of a metal component in ethanol to an aqueous solution ofanother metal component.

The Group VIB metal generally comprises chromium, molybdenum, tungsten,or mixtures thereof. Suitable Group VIII non-noble metals are, e.g.,iron, cobalt, nickel, or mixtures thereof. Preferably, a combination ofmetal components comprising nickel, molybdenum and tungsten or nickel,cobalt, molybdenum and tungsten is applied in the process of the solidroute. If the protic liquid is water, suitable nickel components whichare at least partly in the solid state during contacting comprisewater-insoluble nickel components such as nickel carbonate, nickelhydroxide, nickel phosphate, nickel phosphite, nickel formate, nickelsulfide, nickel molybdate, nickel tungstate, nickel oxide, nickel alloyssuch as nickel-molybdenum alloys, Raney nickel, or mixtures thereof.Suitable molybdenum components, which are at least partly in the solidstate during contacting, comprise water-insoluble molybdenum componentssuch as molybdenum (di- and tri) oxide, molybdenum carbide, molybdenumnitride, aluminum molybdate, molybdic acid (e.g. H₂MoO₄), molybdenumsulfide, or mixtures thereof. Finally, suitable tungsten componentswhich are at least partly in the solid state during contacting comprisetungsten di- and trioxide, tungsten sulfide (WS₂ and WS₃), tungstencarbide, tungstic acid (e.g. H₂WO₄—H₂O, H₂W₂O₃—H₂O), tungsten nitride,aluminum tungstate (also meta-, or polytungstate) or mixtures thereof.These components are generally commercially available or can be preparedby, e.g., precipitation. e.g., nickel carbonate can be prepared from anickel chloride, sulfate, or nitrate solution by adding an appropriateamount of sodium carbonate. It is generally known to the skilled personto choose the precipitation conditions in such a way as to obtain thedesired morphology and texture.

In general, metal components, which mainly contain C, O, and/or Hbesides the metal, are preferred because they are less detrimental tothe environment. Nickel carbonate is a preferred metal component to beadded at least partly in the solid state because when nickel carbonateis applied, CO₂ evolves and positively influences the pH of the reactionmixture. Further, due to the transformation of carbonate into CO₂, thecarbonate does not end up in the wastewater.

Preferred nickel components which are added in the solute state arewater-soluble nickel components, e.g. nickel nitrate, nickel sulfate,nickel acetate, nickel chloride, or mixtures thereof. Preferredmolybdenum and tungsten components which are added in the solute stateare water-soluble molybdenum and tungsten components such as alkalimetal or ammonium molybdate (also peroxo-, di-, tri-, tetra-, hepta-,octa-, or tetradecamolybdate), Mo—P heteropolyanion compounds, Wo-Siheteropolyanion compounds, W—P heteropolyanion compounds, W—Siheteropolyanion compounds, Ni—Mo—W heteropolyanion compounds, Co—Mo—Wheteropolyanion compounds, alkali metal or ammonium tungstates (alsometa-, para-, hexa-, or polytungstate), or mixtures thereof.

Preferred combinations of metal components are nickel carbonate,tungstic acid and molybdenum oxide. Another preferred combination isnickel carbonate, ammonium dimolybdate and ammonium metatungstate. It iswithin the scope of the skilled person to select further suitablecombinations of metal components. It must be noted that nickel carbonatealways comprises a certain amount of hydroxy-groups. It is preferredthat the amount of hydroxy-groups present in the nickel carbonate behigh.

An alternative method of preparing the catalysts used in the practice ofthe present invention is to prepare the bulk catalyst composition by aprocess comprising reacting in a reaction mixture a Group VIII non-noblemetal component in solution and a Group VIB metal component in solutionto obtain a precipitate. As in the case of the solid route, preferably,one Group VIII non-noble metal component is reacted with two Group VIBmetal components. The molar ratio of Group VIB metals to Group VIIInon-noble metals applied in the process of the solution route ispreferably the same as described for the solid route. Suitable Group VIBand Group VIII non-noble metal components are, e.g. those water-solublenickel, molybdenum and tungsten components described above for the solidroute. Further Group VIII non-noble metal components are, e.g., cobaltor iron components. Further Group VIB metal components are, e.g.chromium components. The metal components can be added to the reactionmixture in solution, suspension or as such. If soluble salts are addedas such, they will dissolve in the reaction mixture and subsequently beprecipitated. Suitable Group VIB metal salts which are soluble in waterare ammonium salts such as ammonium dimolybdate, ammonium tri-, tetra-,hepta-, octa-, and tetradeca-molybdate, ammonium para-, meta-, hexa-,and polytungstate, alkali metal salts, silicic acid salts of Group VIBmetals such as molybdic silicic acid, molybdic silicic tungstic acid,tungstic acid, metatungstic acid, pertungstic acid, heteropolyanioncompounds of Mo—P, Mo—Si, W—P, and W—Si. It is also possible to addGroup VIB metal-containing compounds which are not in solution at thetime of addition, but where solution is effected in the reactionmixture. Examples of these compounds are metal compounds which containso much crystal water that upon temperature increase they will dissolvein their own metal water. Further, non-soluble metal salts may be addedin suspension or as such, and solution is effected in the reactionmixture. Suitable non-soluble metals salts are heteropolyanion compoundsof Co—Mo—W (moderately soluble in cold water), heteropolyanion compoundsof Ni—Mo—W (moderately soluble in cold water).

The reaction mixture is reacted to obtain a precipitate. Precipitationis effected by adding a Group VIII non-noble metal salt solution at atemperature and pH at which the Group VIII non-noble metal and the GroupVIB metal precipitate, adding a compound which complexes the metals andreleases the metals for precipitation upon temperature increase or pHchange or adding a Group VIB metal salt solution at a temperature and pHat which the Group VIII non-noble metal and Group VIB metal precipitate,changing the temperature, changing the pH, or lowering the amount of thesolvent. The precipitate obtained with this process appears to have highcatalytic activity. In contrast to the conventional hydroprocessingcatalysts, which usually comprise a carrier impregnated with Group VIIInon-noble metals and Group VIB metals, said precipitate can be usedwithout a support. Unsupported catalyst compositions are usuallyreferred to as bulk catalysts. Changing the pH can be done by addingbase or acid to the reaction mixture, or adding compounds, whichdecompose upon temperature, increase into hydroxide ions or H+ ions thatrespectively increase or decrease the pH. Examples of compounds thatdecompose upon temperature increase and thereby Increase or decrease thepH are urea, nitrites, ammonium cyanate, ammonium hydroxide, andammonium carbonate.

In an illustrative process according to the solution route, solutions ofammonium salts of a Group VIB metal are made and a solution of a GroupVIII non-noble metal nitrate is made. Both solutions are heated to atemperature of approximately 90° C. Ammonium hydroxide is added to theGroup VIB metal solution. The Group VIII non-noble metal solution isadded to the Group VIB metal solution and direct precipitation of theGroup VIB and Group VIII non-noble metal components occurs. This processcan also be conducted at lower temperature and/or decreased pressure orhigher temperature and/or increased pressure.

In another illustrative process according to the solution route, a GroupVIB metal salt, a Group VIII metal salt, and ammonium hydroxide aremixed in solution together and heated so that ammonia is driven off andthe pH is lowered to a pH at which precipitation occurs. For instancewhen nickel, molybdenum, and tungsten components are applied,precipitation typically occurs at a pH below 7.

The bulk catalyst composition can generally be directly shaped intohydroprocessing particles. If the amount of liquid of the bulk catalystcomposition is so high that it cannot be directly subjected to a shapingstep, a solid liquid separation can be performed before shaping.Optionally the bulk catalyst composition, either as such or after solidliquid separation, can be calcined before shaping.

The median diameter of the bulk catalyst particles is at least 50 nm,more preferably at least 100 nm, and preferably not more than 5000 μmand more preferably not more than 3000 μm. Even more preferably, themedian particle diameter lies in the range of 0.1-50 μm and mostpreferably in the range of 0.5-50 μm.

If a binder material is used in the preparation of the catalystcomposition it can be any material that is conventionally applied as abinder in hydroprocessing catalysts. Examples include silica,silica-alumina, such as conventional silica-alumina, silica-coatedalumina and alumina-coated silica, alumina such as (pseudo)boehmite, orgibbsite, titania, zirconia, cationic clays or anionic clays such assaponite, bentonite, kaoline, sepiolite or hydrotalcite, or mixturesthereof. Preferred binders are silica, silica-alumina, alumina, titanic,zirconia, or mixtures thereof. These binders may be applied as such orafter peptization. It is also possible to apply precursors of thesebinders that, during the process of the invention are converted into anyof the above-described binders. Suitable precursors are, e g., alkalimetal aluminates (to obtain an alumina binder), water glass (to obtain asilica binder), a mixture of alkali metal aluminates and water glass (toobtain a silica alumina binder), a mixture of sources of a di-, tri-,and/or tetravalent metal such as a mixture of water-soluble salts ofmagnesium, aluminum and/or silicon (to prepare a cationic clay and/oranionic clay), chlorohydrol, aluminum sulfate, or mixtures thereof.

If desired, the binder material may be composited with a Group VIB metaland/or a Group VIII non-noble metal, prior to being composited with thebulk catalyst composition and/or prior to being added during thepreparation thereof. Compositing the binder material with any of thesemetals may be carried out by impregnation of the solid binder with thesematerials. The person skilled in the art knows suitable impregnationtechniques. If the binder is peptized, it is also possible to carry outthe peptization in the presence of Group VIB and/or Group VIII non-noblemetal components.

Generally, the binder material to be added in the process of theinvention has less catalytic activity than the bulk catalyst compositionor no catalytic activity at all. Consequently, by adding a bindermaterial, the activity of the bulk catalyst composition may be reduced.Therefore, the amount of binder material to be added in the process ofthe invention generally depends on the desired activity of the finalcatalyst composition. Binder amounts from 0-95 wt. % of the totalcomposition can be suitable, depending on the envisaged catalyticapplication. However, to take advantage of the resulting unusual highactivity of the composition of the present invention, binder amounts tobe added are generally in the range of 0.5-75 wt. % of the totalcomposition.

The catalyst composition can be directly shaped. Shaping comprisesextrusion, pelletizing, beading, and/or spray drying. It must be notedthat if the catalyst composition is to be applied in slurry typereactors, fluidized beds, moving beds, expanded beds, or ebullatingbeds, spray drying or beading is generally applied for fixed bedapplications, generally, the catalyst composition is extruded,pelletized and/or beaded. In the latter case, prior to or during theshaping step, any additives that are conventionally used to facilitateshaping can be added. These additives may comprise aluminum stearate,surfactants, graphite or mixtures thereof. These additives can be addedat any stage prior to the shaping step. Further, when alumina is used asa binder, it may be desirable to add acids prior to the shaping stepsuch as nitric acid to increase the mechanical strength of theextrudates.

It is preferred that a binder material is added prior to the shapingstep. Further, it is preferred that the shaping step is carried out inthe presence of a liquid, such as water. Preferably, the amount ofliquid in the extrusion mixture, expressed as LOI is in the range of20-80%.

The resulting shaped catalyst composition can, after an optional dryingstep, be optionally calcined. Calcination however is not essential tothe process of the invention. If a calcination is carried out in theprocess of the invention, it can be done at a temperature of, e.g., from100-600° C. and preferably 350 to 500° C. for a time varying from 0.5 to48 hours. The drying of the shaped particles is generally carried out attemperatures above 100° C.

In a preferred embodiment of the invention, the catalyst composition issubjected to spray drying (flash) drying, milling, kneading, orcombinations thereof prior to shaping. These additional process stepscan be conducted either before or after a binder is added, aftersolid-liquid separation, before or after calcination and subsequent tore-wetting. It is believed that by applying any of the above-describedtechniques of spray drying, (flash) drying, milling, kneading, orcombinations thereof, the degree of mixing between the bulk catalystcomposition and the binder material is improved. This applies to bothcases where the binder material is added before or after the applicationof any of the above-described methods. However, it is generallypreferred to add the binder material prior to spray drying and/or anyalternative technique. If the binder is added subsequent to spray dryingand/or any alternative technique, the resulting composition ispreferably thoroughly mixed by any conventional technique prior toshaping. An advantage of, e.g., spray drying is that no wastewaterstreams are obtained when this technique is applied.

The processes of the present invention for preparing the bulk catalystcompositions may further comprise a sulfidation step. Sulfidation isgenerally carried out by contacting the catalyst composition orprecursors thereof with a sulfur containing compound such as elementarysulfur, hydrogen sulfide or polysulfides. The sulfidation can generallybe carried out subsequently to the preparation of the bulk catalystcomposition but prior to the addition of a binder material, and/orsubsequently to the addition of the binder material but prior tosubjecting the catalyst composition to spray drying and/or anyalternative method, and/or subsequently to subjecting the composition tospray drying and/or any alternative method but prior to shaping, and/orsubsequently to shaping the catalyst composition. It is preferred thatthe sulfidation is not carried out prior to any process step thatreverts the obtained metal sulfides into their oxides. Such processsteps are, e.g., calcination or spray drying or any other hightemperature treatment in the presence of oxygen. Consequently, if thecatalyst composition is subjected to spray drying and/or any alternativetechnique, the sulfidation should be carried out subsequent to theapplication of any of these methods.

Additionally to, or instead of, a sulfidation step, the bulk catalystcomposition may be prepared from at least one metal sulfide. If, e.g.the solid route is applied in step (i), the bulk catalyst component canbe prepared form nickel sulfide and/or molybdenum sulfide and/ortungsten sulfide.

Additional Components for Bulk Catalysts

The sulfided catalyst composition described above can be used as ahydroprocessing catalyst, either alone or in combination with a binder.If the sulfided catalyst composition is a bulk catalyst, then only arelatively small amount of binder may be added. However, if the sulfidedcatalyst composition is a heterogeneous/supported catalyst, then usuallythe binder is a significant portion of the catalyst composition, e.g.,at least about 40 wt %, at least about 50 wt %, at least about 60 wt %,or at least about 70 wt %; additionally or alternately forheterogeneous/supported catalysts, the binder can comprise up to about95 wt % of the catalyst composition, e.g., up to about 90 wt %, up toabout 85 wt %, up to about 80 wt %, up to about 75 wt %, or up to about70 wt %. Non-limiting examples of suitable binder materials can include,but are not limited to, silica, silica-alumina (e.g., conventionalsilica-alumina, silica-coated alumina, alumina-coated silica, or thelike, or a combination thereof), alumina (e.g., boehmite,pseudo-boehmite, gibbsite, or the like, or a combination thereof),titania, zirconia, cationic clays or anionic clays (e.g., saponite,bentonite, kaoline, sepiolite, hydrotalcite, or the like, or acombination thereof), and mixtures thereof. In some preferredembodiments, the binder can include silica, silica-alumina, alumina,titania, zirconia, and mixtures thereof. These binders may be applied assuch or after peptization. It may also be possible to apply precursorsof these binders that, during precursor synthesis, can be converted intoany of the above-described binders. Suitable precursors can include,e.g., alkali metal aluminates (alumina binder), water glass (silicabinder), a mixture of alkali metal aluminates and water glass(silica-alumina binder), a mixture of sources of a di-, tri-, and/ortetravalent metal, such as a mixture of water-soluble salts ofmagnesium, aluminum, and/or silicon (cationic clay and/or anionic clay),chlorohydrol, aluminum sulfate, or mixtures thereof.

Generally, the binder material to be used can have lower catalyticactivity than the remainder of the catalyst composition, or can havesubstantially no catalytic activity at all (less than about 5%, based onthe catalytic activity of the bulk catalyst composition being about100%). Consequently, by using a binder material, the activity of thecatalyst composition may be reduced. Therefore, the amount of bindermaterial to be used, at least in bulk catalysts, can generally depend onthe desired activity of the final catalyst composition. Binder amountsup to about 25 wt % of the total composition can be suitable (whenpresent, from above 0 wt % to about 25 wt %), depending on the envisagedcatalytic application. However, to take advantage of the resultingunusual high activity of bulk catalyst compositions according to theinvention, binder amounts, when added, can generally be from about 0.5wt % to about 20 wt % of the total catalyst composition.

If desired in bulk catalyst cases, the binder material can be compositedwith a source of a Group 6 metal and/or a source of a non-noble Group8-10 metal, prior to being composited with the bulk catalyst compositionand/or prior to being added during the preparation thereof. Compositingthe binder material with any of these metals may be carried out by anyknown means, e.g., impregnation of the (solid) binder material withthese metal(s) sources.

A cracking component may also be added during catalyst preparation. Whenused, the cracking component can represent from about 0.5 wt % to about30 wt %, based on the total weight of the catalyst composition. Thecracking component may serve, for example, as an isomerization enhancer.Conventional cracking components can be used, e.g., a cationic clay, ananionic clay, a zeolite (such as ZSM-5, zeolite Y, ultra-stable zeoliteY, zeolite X, an AlPO, a SAPO, or the like, or a combination thereof),amorphous cracking components (such as silica-alumina or the like), or acombination thereof. It is to be understood that some materials may actas a binder and a cracking component at the same time. For instance,silica-alumina may simultaneously have both a cracking and a bindingfunction.

If desired, the cracking component may be composited with a Group 6metal and/or a Group 8-10 non-noble metal, prior to being compositedwith the catalyst composition and/or prior to being added during thepreparation thereof. Compositing the cracking component with any ofthese metals may be carried out by any known means, e.g., impregnationof the cracking component with these metal(s) sources. When both acracking component and a binder material are used and when compositingof additional metal components is desired on both, the compositing maybe done on each component separately or may be accomplished by combiningthe components and doing a single compositing step.

The selection of particular cracking components, if any, can depend onthe intended catalytic application of the final catalyst composition.For instance, a zeolite can be added if the resulting composition is tobe applied in hydrocracking or fluid catalytic cracking. Other crackingcomponents, such as silica-alumina or cationic clays, can be added ifthe final catalyst composition is to be used in hydrotreatingapplications. The amount of added cracking material can depend on thedesired activity of the final composition and the intended application,and thus, when present, may vary from above 0 wt % to about 80 wt %,based on the total weight of the catalyst composition. In a preferredembodiment, the combination of cracking component and binder materialcan comprise less than 50 wt % of the catalyst composition, for example,less than about 40 wt %, less than about 30 wt %, less than about 20 wt%, less than about 15 wt %, or less than about 10 wt %.

If desired, further materials can be added, in addition to the metalcomponents already added, such as any material that would be addedduring conventional hydroprocessing catalyst preparation. Suitableexamples of such further materials can include, but are not limited to,phosphorus compounds, boron compounds, fluorine-containing compounds,sources of additional transition metals, sources of rare earth metals,fillers, or mixtures thereof.

Hydrotreating and Hydrocracking

After deasphalting, the deasphalted oil (and any additional fractionscombined with the deasphalted oil) can undergo further processing toform lubricant base stocks. This can include hydrotreatment and/orhydrocracking to remove heteroatoms to desired levels, reduce ConradsonCarbon content, and/or provide viscosity index (VI) uplift. Depending onthe aspect, a deasphalted oil can be hydroprocessed by hydrotreating,hydrocracking, or hydrotreating and hydrocracking. Optionally, one ormore catalyst beds and/or stages of demetallization catalyst can beincluded prior to the initial bed of hydrotreating and/or hydrocrackingcatalyst. Optionally, the hydroprocessing can further include exposingthe deasphalted oil to a base metal aromatic saturation catalyst. It isnoted that a base metal aromatic saturation catalyst can sometimes besimilar to a lower activity hydrotreating catalyst.

The deasphalted oil can be hydrotreated and/or hydrocracked with littleor no solvent extraction being performed prior to and/or after thedeasphalting. As a result, the deasphalted oil feed for hydrotreatmentand/or hydrocracking can have a substantial aromatics content. Invarious aspects, the aromatics content of the deasphalted oil feed canbe at least 50 wt %, or at least 55 wt %, or at least 60 wt %, or atleast 65 wt %, or at least 70 wt %, or at least 75 wt %, such as up to90 wt % or more. Additionally or alternately, the saturates content ofthe deasphalted oil feed can be 50 wt % or less, or 45 wt % or less, or40 wt % or less, or 35 wt % or less, or 30 wt % or less, or 25 wt % orless, such as down to 10 wt % or less. In this discussion and the claimsbelow, the aromatics content and/or the saturates content of a fractioncan be determined based on ASTM D7419.

The reaction conditions during demetallization and/or hydrotreatmentand/or hydrocracking of the deasphalted oil (and optional vacuum gas oilco-feed) can be selected to generate a desired level of conversion of afeed. Any convenient type of reactor, such as fixed bed (for exampletrickle bed) reactors can be used. Conversion of the feed can be definedin terms of conversion of molecules that boil above a temperaturethreshold to molecules below that threshold. The conversion temperaturecan be any convenient temperature, such as ˜700° F. (370° C.) or 1050°F. (566° C.). The amount of conversion can correspond to the totalconversion of molecules within the combined hydrotreatment andhydrocracking stages for the deasphalted oil. Suitable amounts ofconversion of molecules boiling above 1050° F. (566° C.) to moleculesboiling below 566° C. include 30 wt % to 90 wt % conversion relative to566° C., or 30 wt % to 80 wt %, or 30 wt % to 70 wt %, or 40 wt % to 90wt %, or 40 wt % to 80 wt %, or 40 wt % to 70 wt %, or 50 wt % to 90 wt%, or 50 wt % to 80 wt %, or 50 wt % to 70 wt %. In particular, theamount of conversion relative to 566° C. can be 30 wt % to 90 wt %, or30 wt % to 70 wt %, or 50 wt % to 90 wt %. Additionally or alternately,suitable amounts of conversion of molecules boiling above ˜700° F. (370°C.) to molecules boiling below 370° C. include 10 wt % to 70 wt %conversion relative to 370° C., or 10 wt % to 60 wt %, or 10 wt % to 50wt %, or 20 wt % to 70 wt %, or 20 wt % to 60 wt %, or 20 wt % to 50 wt%, or 30 wt % to 70 wt %, or 30 wt % to 60 wt %, or 30 wt % to 50 wt %.In particular, the amount of conversion relative to 370° C. can be 10 wt% to 70 wt %, or 20 wt % to 50 wt %, or 30 wt % to 60 wt %.

The hydroprocessed deasphalted oil can also be characterized based onthe product quality. After hydroprocessing (hydrotreating and/orhydrocracking), the hydroprocessed deasphalted oil can have a sulfurcontent of 200 wppm or less, or 100 wppm or less, or 50 wppm or less(such as down to ˜0 wppm). Additionally or alternately, thehydroprocessed deasphalted oil can have a nitrogen content of 200 wppmor less, or 100 wppm or less, or 50 wppm or less (such as down to ˜0wppm). Additionally or alternately, the hydroprocessed deasphalted oilcan have a Conradson Carbon residue content of 1.5 wt % or less, or 1.0wt % or less, or 0.7 wt % or less, or 0.1 wt % or less, or 0.02 wt % orless (such as down to ˜0 wt %). Conradson Carbon residue content can bedetermined according to ASTM D4530.

In various aspects, a feed can initially be exposed to a demetallizationcatalyst prior to exposing the feed to a hydrotreating catalyst.Deasphalted oils can have metals concentrations (Ni+V+Fe) on the orderof 10-100 wppm. Exposing a conventional hydrotreating catalyst to a feedhaving a metals content of 10 wppm or more can lead to catalystdeactivation at a faster rate than may desirable in a commercialsetting. Exposing a metal containing feed to a demetallization catalystprior to the hydrotreating catalyst can allow at least a portion of themetals to be removed by the demetallization catalyst, which can reduceor minimize the deactivation of the hydrotreating catalyst and/or othersubsequent catalysts in the process flow. Commercially availabledemetallization catalysts can be suitable, such as large pore amorphousoxide catalysts that may optionally include Group VI and/or Group VIIInon-noble metals to provide some hydrogenation activity.

In various aspects, the deasphalted oil can be exposed to ahydrotreating catalyst under effective hydrotreating conditions. Thecatalysts used can include conventional hydroprocessing catalysts, suchas those comprising at least one Group VIII non-noble metal (Columns8-10 of IUPAC periodic table), preferably Fe, Co, and/or Ni, such as Coand/or Ni; and at least one Group VI metal (Column 6 of IUPAC periodictable), preferably Mo and/or W. Such hydroprocessing catalystsoptionally include transition metal sulfides that are impregnated ordispersed on a refractory support or carrier such as alumina and/orsilica. The support or carrier itself typically has nosignificant/measurable catalytic activity. Substantially carrier- orsupport-free catalysts, commonly referred to as bulk catalysts,generally have higher volumetric activities than their supportedcounterparts.

The catalysts can either be in bulk form or in supported form. Inaddition to alumina and/or silica, other suitable support/carriermaterials can include, but are not limited to, zeolites, titania,silica-titania, and titania-alumina. Suitable aluminas are porousaluminas such as gamma or eta having average pore sizes from 50 to 200Å, or 75 to 150 Å; a surface area from 100 to 300 m²/g, or 150 to 250m²/g; and a pore volume of from 0.25 to 1.0 cm³/g, or 0.35 to 0.8 cm³/g.More generally, any convenient size, shape, and/or pore sizedistribution for a catalyst suitable for hydrotreatment of a distillate(including lubricant base stock) boiling range feed in a conventionalmanner may be used. Preferably, the support or carrier material is anamorphous support, such as a refractory oxide. Preferably, the supportor carrier material can be free or substantially free of the presence ofmolecular sieve, where substantially free of molecular sieve is definedas having a content of molecular sieve of less than about 0.01 wt %.

The at least one Group VIII non-noble metal, in oxide form, cantypically be present in an amount ranging from about 2 wt % to about 40wt %, preferably from about 4 wt % to about 15 wt %. The at least oneGroup VI metal, in oxide form, can typically be present in an amountranging from about 2 wt % to about 70 wt %, preferably for supportedcatalysts from about 6 wt % to about 40 wt % or from about 10 wt % toabout 30 wt %. These weight percents are based on the total weight ofthe catalyst. Suitable metal catalysts include cobalt/molybdenum (1-10%Co as oxide, 10-40% Mo as oxide), nickel/molybdenum (1-10% Ni as oxide,10-40% Co as oxide), or nickel/tungsten (1-10% Ni as oxide, 10-40% W asoxide) on alumina, silica, silica-alumina, or titania.

The hydrotreatment is carried out in the presence of hydrogen. Ahydrogen stream is, therefore, fed or injected into a vessel or reactionzone or hydroprocessing zone in which the hydroprocessing catalyst islocated. Hydrogen, which is contained in a hydrogen “treat gas,” isprovided to the reaction zone. Treat gas, as referred to in thisinvention, can be either pure hydrogen or a hydrogen-containing gas,which is a gas stream containing hydrogen in an amount that issufficient for the intended reaction(s), optionally including one ormore other gasses (e.g., nitrogen and light hydrocarbons such asmethane). The treat gas stream introduced into a reaction stage willpreferably contain at least about 50 vol. % and more preferably at leastabout 75 vol. % hydrogen. Optionally, the hydrogen treat gas can besubstantially free (less than 1 vol %) of impurities such as H₂S and NH₃and/or such impurities can be substantially removed from a treat gasprior to use.

Hydrogen can be supplied at a rate of from about 100 SCF/B (standardcubic feet of hydrogen per barrel of feed) (17 Nm³/m³) to about 10000SCF/B (1700 Nm³/m³). Preferably, the hydrogen is provided in a range offrom about 200 SCF/B (34 Nm³/m³) to about 2500 SCF/B (420 Nm³/m³).Hydrogen can be supplied co-currently with the input feed to thehydrotreatment reactor and/or reaction zone or separately via a separategas conduit to the hydrotreatment zone.

Hydrotreating conditions can include temperatures of 200° C. to 450° C.,or 315° C. to 425° C.; pressures of 250 psig (1.8 MPag) to 5000 psig(34.6 MPag) or 300 psig (2.1 MPag) to 3000 psig (20.8 MPag); liquidhourly space velocities (LHSV) of 0.1 hr⁻¹ to 10 hr⁻¹; and hydrogentreat rates of 200 scf/B (35.6 m³/m³) to 10,000 scf/B (1781 m³/m³), or500 (89 m³/m³) to 10,000 scf/B (1781 m³/m³).

In various aspects, the deasphalted oil can be exposed to ahydrocracking catalyst under effective hydrocracking conditions.Hydrocracking catalysts typically contain sulfided base metals on acidicsupports, such as amorphous silica alumina, cracking zeolites such asUSY, or acidified alumina. Often these acidic supports are mixed orbound with other metal oxides such as alumina, titania or silica.Examples of suitable acidic supports include acidic molecular sieves,such as zeolites or silicoaluminophophates. One example of suitablezeolite is USY, such as a USY zeolite with cell size of 24.30 Angstromsor less. Additionally or alternately, the catalyst can be a low aciditymolecular sieve, such as a USY zeolite with a Si to Al ratio of at leastabout 20, and preferably at least about 40 or 50. ZSM-48, such as ZSM-48with a SiO₂ to Al₂O₃ ratio of about 110 or less, such as about 90 orless, is another example of a potentially suitable hydrocrackingcatalyst. Still another option is to use a combination of USY andZSM-48. Still other options include using one or more of zeolite Beta,ZSM-5, ZSM-35, or ZSM-23, either alone or in combination with a USYcatalyst. Non-limiting examples of metals for hydrocracking catalystsinclude metals or combinations of metals that include at least one GroupVIII metal, such as nickel, nickel-cobalt-molybdenum, cobalt-molybdenum,nickel-tungsten, nickel-molybdenum, and/or nickel-molybdenum-tungsten.Additionally or alternately, hydrocracking catalysts with noble metalscan also be used. Non-limiting examples of noble metal catalysts includethose based on platinum and/or palladium. Support materials which may beused for both the noble and non-noble metal catalysts can comprise arefractory oxide material such as alumina, silica, alumina-silica,kieselguhr, diatomaceous earth, magnesia, zirconia, or combinationsthereof, with alumina, silica, alumina-silica being the most common (andpreferred, in one embodiment).

When only one hydrogenation metal is present on a hydrocrackingcatalyst, the amount of that hydrogenation metal can be at least about0.1 wt % based on the total weight of the catalyst, for example at leastabout 0.5 wt % or at least about 0.6 wt %. Additionally or alternatelywhen only one hydrogenation metal is present, the amount of thathydrogenation metal can be about 5.0 wt % or less based on the totalweight of the catalyst, for example about 3.5 wt % or less, about 2.5 wt% or less, about 1.5 wt % or less, about 1.0 wt % or less, about 0.9 wt% or less, about 0.75 wt % or less, or about 0.6 wt % or less. Furtheradditionally or alternately when more than one hydrogenation metal ispresent, the collective amount of hydrogenation metals can be at leastabout 0.1 wt % based on the total weight of the catalyst, for example atleast about 0.25 wt %, at least about 0.5 wt %, at least about 0.6 wt %,at least about 0.75 wt %, or at least about 1 wt %. Still furtheradditionally or alternately when more than one hydrogenation metal ispresent, the collective amount of hydrogenation metals can be about 35wt % or less based on the total weight of the catalyst, for exampleabout 30 wt % or less, about 25 wt % or less, about 20 wt % or less,about 15 wt % or less, about 10 wt % or less, or about 5 wt % or less.In embodiments wherein the supported metal comprises a noble metal, theamount of noble metal(s) is typically less than about 2 wt %, forexample less than about 1 wt %, about 0.9 wt % or less, about 0.75 wt %or less, or about 0.6 wt % or less. It is noted that hydrocracking undersour conditions is typically performed using a base metal (or metals) asthe hydrogenation metal.

In various aspects, the conditions selected for hydrocracking forlubricant base stock production can depend on the desired level ofconversion, the level of contaminants in the input feed to thehydrocracking stage, and potentially other factors. For example,hydrocracking conditions in a single stage, or in the first stage and/orthe second stage of a multi-stage system, can be selected to achieve adesired level of conversion in the reaction system. Hydrocrackingconditions can be referred to as sour conditions or sweet conditions,depending on the level of sulfur and/or nitrogen present within a feed.For example, a feed with 100 wppm or less of sulfur and 50 wppm or lessof nitrogen, preferably less than 25 wppm sulfur and/or less than 10wppm of nitrogen, represent a feed for hydrocracking under sweetconditions. In various aspects, hydrocracking can be performed on athermally cracked resid, such as a deasphalted oil derived from athermally cracked resid. In some aspects, such as aspects where anoptional hydrotreating step is used prior to hydrocracking, thethermally cracked resid may correspond to a sweet feed. In otheraspects, the thermally cracked resid may represent a feed forhydrocracking under sour conditions.

A hydrocracking process under sour conditions can be carried out attemperatures of about 550° F. (288° C.) to about 840° F. (449° C.),hydrogen partial pressures of from about 1500 psig to about 5000 psig(10.3 MPag to 34.6 MPag), liquid hourly space velocities of from 0.05h⁻¹ to 10 h⁻¹, and hydrogen treat gas rates of from 35.6 m³/m³ to 1781m³/m³ (200 SCF/B to 10,000 SCF/B). In other embodiments, the conditionscan include temperatures in the range of about 600° F. (343° C.) toabout 815° F. (435° C.), hydrogen partial pressures of from about 1500psig to about 3000 psig (10.3 MPag-20.9 MPag), and hydrogen treat gasrates of from about 213 m³/m³ to about 1068 m³/m³ (1200 SCF/B to 6000SCF/B). The LHSV can be from about 0.25 h⁻¹ to about 50 h⁻¹, or fromabout 0.5 h⁻¹ to about 20 h⁻¹, preferably from about 1.0 h⁻¹ to about4.0 h⁻¹.

In some aspects, a portion of the hydrocracking catalyst can becontained in a second reactor stage. In such aspects, a first reactionstage of the hydroprocessing reaction system can include one or morehydrotreating and/or hydrocracking catalysts. The conditions in thefirst reaction stage can be suitable for reducing the sulfur and/ornitrogen content of the feedstock. A separator can then be used inbetween the first and second stages of the reaction system to remove gasphase sulfur and nitrogen contaminants. One option for the separator isto simply perform a gas-liquid separation to remove contaminant. Anotheroption is to use a separator such as a flash separator that can performa separation at a higher temperature. Such a high temperature separatorcan be used, for example, to separate the feed into a portion boilingbelow a temperature cut point, such as about 350° F. (177° C.) or about400° F. (204° C.), and a portion boiling above the temperature cutpoint. In this type of separation, the naphtha boiling range portion ofthe effluent from the first reaction stage can also be removed, thusreducing the volume of effluent that is processed in the second or othersubsequent stages. Of course, any low boiling contaminants in theeffluent from the first stage would also be separated into the portionboiling below the temperature cut point. If sufficient contaminantremoval is performed in the first stage, the second stage can beoperated as a “sweet” or low contaminant stage.

Still another option can be to use a separator between the first andsecond stages of the hydroprocessing reaction system that can alsoperform at least a partial fractionation of the effluent from the firststage. In this type of aspect, the effluent from the firsthydroprocessing stage can be separated into at least a portion boilingbelow the distillate (such as diesel) fuel range, a portion boiling inthe distillate fuel range, and a portion boiling above the distillatefuel range. The distillate fuel range can be defined based on aconventional diesel boiling range, such as having a lower end cut pointtemperature of at least about 350° F. (177° C.) or at least about 400°F. (204° C.) to having an upper end cut point temperature of about 700°F. (371° C.) or less or 650° F. (343° C.) or less. Optionally, thedistillate fuel range can be extended to include additional kerosene,such as by selecting a lower end cut point temperature of at least about300° F. (149° C.).

In aspects where the inter-stage separator is also used to produce adistillate fuel fraction, the portion boiling below the distillate fuelfraction includes, naphtha boiling range molecules, light ends, andcontaminants such as H₂S. These different products can be separated fromeach other in any convenient manner. Similarly, one or more distillatefuel fractions can be formed, if desired, from the distillate boilingrange fraction. The portion boiling above the distillate fuel rangerepresents the potential lubricant base stocks. In such aspects, theportion boiling above the distillate fuel range is subjected to furtherhydroprocessing in a second hydroprocessing stage.

A hydrocracking process under sweet conditions can be performed underconditions similar to those used for a sour hydrocracking process, orthe conditions can be different. In an embodiment, the conditions in asweet hydrocracking stage can have less severe conditions than ahydrocracking process in a sour stage. Suitable hydrocracking conditionsfor a non-sour stage can include, but are not limited to, conditionssimilar to a first or sour stage. Suitable hydrocracking conditions caninclude temperatures of about 500° F. (260° C.) to about 840° F. (449°C.), hydrogen partial pressures of from about 1500 psig to about 5000psig (10.3 MPag to 34.6 MPag), liquid hourly space velocities of from0.05 h⁻¹ to 10 h⁻¹, and hydrogen treat gas rates of from 35.6 m³/m³ to1781 m³/m³ (200 SCF/B to 10,000 SCF/B). In other embodiments, theconditions can include temperatures in the range of about 600° F. (343°C.) to about 815° F. (435° C.), hydrogen partial pressures of from about1500 psig to about 3000 psig (10.3 MPag-20.9 MPag), and hydrogen treatgas rates of from about 213 m³/m³ to about 1068 m³/m³ (1200 SCF/B to6000 SCF/B). The LHSV can be from about 0.25 h⁻¹ to about 50 h⁻¹, orfrom about 0.5 h⁻¹ to about 20 h⁻¹, preferably from about 1.0 h⁻¹ toabout 4.0 h⁻¹.

In still another aspect, the same conditions can be used forhydrotreating and hydrocracking beds or stages, such as usinghydrotreating conditions for both or using hydrocracking conditions forboth. In yet another embodiment, the pressure for the hydrotreating andhydrocracking beds or stages can be the same.

In yet another aspect, a hydroprocessing reaction system may includemore than one hydrocracking stage. If multiple hydrocracking stages arepresent, at least one hydrocracking stage can have effectivehydrocracking conditions as described above, including a hydrogenpartial pressure of at least about 1500 psig (10.3 MPag). In such anaspect, other hydrocracking processes can be performed under conditionsthat may include lower hydrogen partial pressures. Suitablehydrocracking conditions for an additional hydrocracking stage caninclude, but are not limited to, temperatures of about 500° F. (260° C.)to about 840° F. (449° C.), hydrogen partial pressures of from about 250psig to about 5000 psig (1.8 MPag to 34.6 MPag), liquid hourly spacevelocities of from 0.05 h⁻¹ to 10 h⁻¹, and hydrogen treat gas rates offrom 35.6 m³/m³ to 1781 m³/m³ (200 SCF/B to 10,000 SCF/B). In otherembodiments, the conditions for an additional hydrocracking stage caninclude temperatures in the range of about 600° F. (343° C.) to about815° F. (435° C.), hydrogen partial pressures of from about 500 psig toabout 3000 psig (3.5 MPag-20.9 MPag), and hydrogen treat gas rates offrom about 213 m³/m³ to about 1068 m³/m³ (1200 SCF/B to 6000 SCF/B). TheLHSV can be from about 0.25 h⁻¹ to about 50 h⁻¹, or from about 0.5 h⁻¹to about 20 h⁻¹, and preferably from about 1.0 h⁻¹ to about 4.0 h⁻¹.

Additional Hydroprocessing—Hydrocracking, Catalytic Dewaxing, andHydrofinishing

In some alternative aspects, at least a lubricant boiling range portionof the hydroprocessed deasphalted oil can be exposed to furtherhydroprocessing (including catalytic dewaxing) to form either Group Iand/or Group II base stocks, including Group I and/or Group II brightstock. In some aspects, a first lubricant boiling range portion of thehydroprocessed deasphalted oil can be solvent dewaxed as described abovewhile a second lubricant boiling range portion can be exposed to furtherhydroprocessing. In other aspects, only solvent dewaxing or only furtherhydroprocessing can be used to treat a lubricant boiling range portionof the hydroprocessed deasphalted oil.

Optionally, the further hydroprocessing of the lubricant boiling rangeportion of the hydroprocessed deasphalted oil can also include exposureto hydrocracking conditions before and/or after the exposure to thecatalytic dewaxing conditions. At this point in the process, thehydrocracking can be considered “sweet” hydrocracking, as thehydroprocessed deasphalted oil can have a sulfur content of 200 wppm orless.

Suitable hydrocracking conditions can include exposing the feed to ahydrocracking catalyst as previously described above. Optionally, it canbe preferable to use a USY zeolite with a silica to alumina ratio of atleast 30 and a unit cell size of less than 24.32 Angstroms as thezeolite for the hydrocracking catalyst, in order to improve the VIuplift from hydrocracking and/or to improve the ratio of distillate fuelyield to naphtha fuel yield in the fuels boiling range product.

Suitable hydrocracking conditions can also include temperatures of about500° F. (260° C.) to about 840° F. (449° C.), hydrogen partial pressuresof from about 1500 psig to about 5000 psig (10.3 MPag to 34.6 MPag),liquid hourly space velocities of from 0.05 h⁻¹ to 10 h⁻¹, and hydrogentreat gas rates of from 35.6 m³/m³ to 1781 m³/m³ (200 SCF/B to 10,000SCF/B). In other embodiments, the conditions can include temperatures inthe range of about 600° F. (343° C.) to about 815° F. (435° C.),hydrogen partial pressures of from about 1500 psig to about 3000 psig(10.3 MPag-20.9 MPag), and hydrogen treat gas rates of from about 213m³/m³ to about 1068 m³/m³ (1200 SCF/B to 6000 SCF/B). The LHSV can befrom about 0.25 h⁻¹ to about 50 h⁻¹, or from about 0.5 h⁻¹ to about 20h⁻¹, and preferably from about 1.0 h⁻¹ to about 4.0 h⁻¹.

For catalytic dewaxing, suitable dewaxing catalysts can includemolecular sieves such as crystalline aluminosilicates (zeolites). In anembodiment, the molecular sieve can comprise, consist essentially of, orbe ZSM-22, ZSM-23, ZSM-48. Optionally but preferably, molecular sievesthat are selective for dewaxing by isomerization as opposed to crackingcan be used, such as ZSM-48, ZSM-23, or a combination thereof.Additionally or alternately, the molecular sieve can comprise, consistessentially of, or be a 10-member ring 1-D molecular sieve, such asEU-2, EU-11, ZBM-30, ZSM-48, or ZSM-23. ZSM-48 is most preferred. Notethat a zeolite having the ZSM-23 structure with a silica to aluminaratio of from about 20:1 to about 40:1 can sometimes be referred to asSSZ-32. Optionally but preferably, the dewaxing catalyst can include abinder for the molecular sieve, such as alumina, titania, silica,silica-alumina, zirconia, or a combination thereof, for example aluminaand/or titania or silica and/or zirconia and/or titania.

Preferably, the dewaxing catalysts used in processes according to theinvention are catalysts with a low ratio of silica to alumina. Forexample, for ZSM-48, the ratio of silica to alumina in the zeolite canbe about 100:1 or less, such as about 90:1 or less, or about 75:1 orless, or about 70:1 or less. Additionally or alternately, the ratio ofsilica to alumina in the ZSM-48 can be at least about 50:1, such as atleast about 60:1, or at least about 65:1.

In various embodiments, the catalysts according to the invention furtherinclude a metal hydrogenation component. The metal hydrogenationcomponent is typically a Group VI and/or a Group VIII metal. Preferably,the metal hydrogenation component can be a combination of a non-nobleGroup VIII metal with a Group VI metal. Suitable combinations caninclude Ni, Co, or Fe with Mo or W, preferably Ni with Mo or W.

The metal hydrogenation component may be added to the catalyst in anyconvenient manner. One technique for adding the metal hydrogenationcomponent is by incipient wetness. For example, after combining azeolite and a binder, the combined zeolite and binder can be extrudedinto catalyst particles. These catalyst particles can then be exposed toa solution containing a suitable metal precursor. Alternatively, metalcan be added to the catalyst by ion exchange, where a metal precursor isadded to a mixture of zeolite (or zeolite and binder) prior toextrusion.

The amount of metal in the catalyst can be at least 0.1 wt % based oncatalyst, or at least 0.5 wt %, or at least 1.0 wt %, or at least 2.5 wt%, or at least 5.0 wt %, based on catalyst. The amount of metal in thecatalyst can be 20 wt % or less based on catalyst, or 10 wt % or less,or 5 wt % or less, or 2.5 wt % or less, or 1 wt % or less. Forembodiments where the metal is a combination of a non-noble Group VIIImetal with a Group VI metal, the combined amount of metal can be from0.5 wt % to 20 wt %, or 1 wt % to 15 wt %, or 2.5 wt % to 10 wt %.

The dewaxing catalysts useful in processes according to the inventioncan also include a binder. In some embodiments, the dewaxing catalystsused in process according to the invention are formulated using a lowsurface area binder, a low surface area binder represents a binder witha surface area of 100 m²/g or less, or 80 m²/g or less, or 70 m²/g orless. Additionally or alternately, the binder can have a surface area ofat least about 25 m²/g. The amount of zeolite in a catalyst formulatedusing a binder can be from about 30 wt % zeolite to 90 wt % zeoliterelative to the combined weight of binder and zeolite. Preferably, theamount of zeolite is at least about 50 wt % of the combined weight ofzeolite and binder, such as at least about 60 wt % or from about 65 wt %to about 80 wt %.

Without being bound by any particular theory, it is believed that use ofa low surface area binder reduces the amount of binder surface areaavailable for the hydrogenation metals supported on the catalyst. Thisleads to an increase in the amount of hydrogenation metals that aresupported within the pores of the molecular sieve in the catalyst.

A zeolite can be combined with binder in any convenient manner. Forexample, a bound catalyst can be produced by starting with powders ofboth the zeolite and binder, combining and mulling the powders withadded water to form a mixture, and then extruding the mixture to producea bound catalyst of a desired size. Extrusion aids can also be used tomodify the extrusion flow properties of the zeolite and binder mixture.The amount of framework alumina in the catalyst may range from 0.1 to3.33 wt %, or 0.1 to 2.7 wt %, or 0.2 to 2 wt %, or 0.3 to 1 wt %.

Effective conditions for catalytic dewaxing of a feedstock in thepresence of a dewaxing catalyst can include a temperature of from 280°C. to 450° C., preferably 343° C. to 435° C., a hydrogen partialpressure of from 3.5 MPag to 34.6 MPag (500 psig to 5000 psig),preferably 4.8 MPag to 20.8 MPag, and a hydrogen circulation rate offrom 178 m³/m³ (1000 SCF/B) to 1781 m³/m³ (10,000 scf/B), preferably 213m³/m³ (1200 SCF/B) to 1068 m³/m³ (6000 SCF/B). The LHSV can be fromabout 0.2 to about 10 h⁻¹, such as from about 0.5 h⁻¹ to about 5 and/orfrom about 1 h⁻¹ to about 4 h⁻¹.

Before and/or after catalytic dewaxing, the hydroprocessed deasphaltedoil (i.e., at least a lubricant boiling range portion thereof) canoptionally be exposed to an aromatic saturation catalyst, which canalternatively be referred to as a hydrofinishing catalyst. Exposure tothe aromatic saturation catalyst can occur either before or afterfractionation. If aromatic saturation occurs after fractionation, thearomatic saturation can be performed on one or more portions of thefractionated product. Alternatively, the entire effluent from the lasthydrocracking or dewaxing process can be hydrofinished and/or undergoaromatic saturation.

Hydrofinishing and/or aromatic saturation catalysts can includecatalysts containing Group VI metals, Group VIII metals, and mixturesthereof. In an embodiment, preferred metals include at least one metalsulfide having a strong hydrogenation function. In another embodiment,the hydrofinishing catalyst can include a Group VIII noble metal, suchas Pt, Pd, or a combination thereof. The mixture of metals may also bepresent as bulk metal catalysts wherein the amount of metal is about 30wt. % or greater based on catalyst. For supported hydrotreatingcatalysts, suitable metal oxide supports include low acidic oxides suchas silica, alumina, silica-aluminas or titania, preferably alumina. Thepreferred hydrofinishing catalysts for aromatic saturation will compriseat least one metal having relatively strong hydrogenation function on aporous support. Typical support materials include amorphous orcrystalline oxide materials such as alumina, silica, and silica-alumina.The support materials may also be modified, such as by halogenation, orin particular fluorination. The metal content of the catalyst is oftenas high as about 20 weight percent for non-noble metals. In anembodiment, a preferred hydrofinishing catalyst can include acrystalline material belonging to the M41S class or family of catalysts.The M41S family of catalysts are mesoporous materials having high silicacontent. Examples include MCM-41, MCM-48 and MCM-50. A preferred memberof this class is MCM-41.

Hydrofinishing conditions can include temperatures from about 125° C. toabout 425° C., preferably about 180° C. to about 280° C., a hydrogenpartial pressure from about 500 psig (3.4 MPa) to about 3000 psig (20.7MPa), preferably about 1500 psig (10.3 MPa) to about 2500 psig (17.2MPa), and liquid hourly space velocity from about 0.1 hr⁻¹ to about 5hr⁻¹ LHSV, preferably about 0.5 hr⁻¹ to about 1.5 hr⁻¹. Additionally, ahydrogen treat gas rate of from 35.6 m³/m³ to 1781 m³/m³ (200 SCF/B to10,000 SCF/B) can be used.

Solvent Processing of Catalytically Dewaxed Effluent or Input Flow toCatalytic Dewaxing

For deasphalted oils derived from propane deasphalting, the furtherhydroprocessing (including catalytic dewaxing) can be sufficient to formlubricant base stocks with low haze formation and unexpectedcompositional properties. For deasphalted oils derived from C₄₊deasphalting, after the further hydroprocessing (including catalyticdewaxing), the resulting catalytically dewaxed effluent can be solventprocessed to form one or more lubricant base stock products with areduced or eliminated tendency to form haze. The type of solventprocessing can be dependent on the nature of the initial hydroprocessing(hydrotreatment and/or hydrocracking) and the nature of the furtherhydroprocessing (including dewaxing).

In aspects where the initial hydroprocessing is less severe,corresponding to 10 wt % to 40 wt % conversion relative to ˜700° F.(370° C.), the subsequent solvent processing can correspond to solventdewaxing. The solvent dewaxing can be performed in a manner similar tothe solvent dewaxing described above. However, this solvent dewaxing canbe used to produce a Group II lubricant base stock. In some aspects,when the initial hydroprocessing corresponds to 10 wt % to 40 wt %conversion relative to 370° C., the catalytic dewaxing during furtherhydroprocessing can also be performed at lower severity, so that atleast 6 wt % wax remains in the catalytically dewaxed effluent, or atleast 8 wt %, or at least 10 wt %, or at least 12 wt %, or at least 15wt %, such as up to 20 wt %. The solvent dewaxing can then be used toreduce the wax content in the catalytically dewaxed effluent by 2 wt %to 10 wt %. This can produce a solvent dewaxed oil product having a waxcontent of 0.1 wt % to 12 wt %, or 0.1 wt % to 10 wt %, or 0.1 wt % to 8wt %, or 0.1 wt % to 6 wt %, or 1 wt % to 12 wt %, or 1 wt % to 10 wt %,or 1 wt % to 8 wt %, or 4 wt % to 12 wt %, or 4 wt % to 10 wt %, or 4 wt% to 8 wt %, or 6 wt % to 12 wt %, or 6 wt % to 10 wt %. In particular,the solvent dewaxed oil can have a wax content of 0.1 wt % to 12 wt %,or 0.1 wt % to 6 wt %, or 1 wt % to 10 wt %, or 4 wt % to 12 wt %.

In other aspects, the subsequent solvent processing can correspond tosolvent extraction. Solvent extraction can be used to reduce thearomatics content and/or the amount of polar molecules. The solventextraction process selectively dissolves aromatic components to form anaromatics-rich extract phase while leaving the more paraffiniccomponents in an aromatics-poor raffinate phase. Naphthenes aredistributed between the extract and raffinate phases. Typical solventsfor solvent extraction include phenol, furfural and N-methylpyrrolidone. By controlling the solvent to oil ratio, extractiontemperature and method of contacting distillate to be extracted withsolvent, one can control the degree of separation between the extractand raffinate phases. Any convenient type of liquid-liquid extractor canbe used, such as a counter-current liquid-liquid extractor. Depending onthe initial concentration of aromatics in the deasphalted oil, theraffinate phase can have an aromatics content of 5 wt % to 25 wt %. Fortypical feeds, the aromatics contents can be at least 10 wt %.

Optionally, the raffinate from the solvent extraction can beunder-extracted. In such aspects, the extraction is carried out underconditions such that the raffinate yield is maximized while stillremoving most of the lowest quality molecules from the feed. Raffinateyield may be maximized by controlling extraction conditions, forexample, by lowering the solvent to oil treat ratio and/or decreasingthe extraction temperature. In various aspects, the raffinate yield fromsolvent extraction can be at least 40 wt %, or at least 50 wt %, or atleast 60 wt %, or at least 70 wt %.

The solvent processed oil (solvent dewaxed or solvent extracted) canhave a pour point of −6° C. or less, or −10° C. or less, or −15° C. orless, or −20° C. or less, depending on the nature of the targetlubricant base stock product. Additionally or alternately, the solventprocessed oil (solvent dewaxed or solvent extracted) can have a cloudpoint of −2° C. or less, or −5° C. or less, or −10° C. or less,depending on the nature of the target lubricant base stock product. Pourpoints and cloud points can be determined according to ASTM D97 and ASTMD2500, respectively. The resulting solvent processed oil can be suitablefor use in forming one or more types of Group II base stocks. Theresulting solvent dewaxed oil can have a viscosity index of at least 80,or at least 90, or at least 95, or at least 100, or at least 110, or atleast 120. Viscosity index can be determined according to ASTM D2270.Preferably, at least 10 wt % of the resulting solvent processed oil (orat least 20 wt %, or at least 30 wt %) can correspond to a Group IIbright stock having a kinematic viscosity at 100° C. of at least 14 cSt,or at least 15 cSt, or at least 20 cSt, or at least 25 cSt, or at least30 cSt, or at least 32 cSt, such as up to 50 cSt or more. Additionallyor alternately, the Group II bright stock can have a kinematic viscosityat 40° C. of at least 300 cSt, or at least 320 cSt, or at least 340 cSt,or at least 350 cSt, such as up to 500 cSt or more. Kinematic viscositycan be determined according to ASTM D445. Additionally or alternately,the Conradson Carbon residue content can be about 0.1 wt % or less, orabout 0.02 wt % or less. Conradson Carbon residue content can bedetermined according to ASTM D4530. Additionally or alternately, theresulting base stock can have a turbidity of at least 1.5 (incombination with a cloud point of less than 0° C.), or can have aturbidity of at least 2.0, and/or can have a turbidity of 4.0 or less,or 3.5 or less, or 3.0 or less. In particular, the turbidity can be 1.5to 4.0, or 1.5 to 3.0, or 2.0 to 4.0, or 2.0 to 3.5.

The reduced or eliminated tendency to form haze for the lubricant basestocks formed from the solvent processed oil can be demonstrated by thereduced or minimized difference between the cloud point temperature andpour point temperature for the lubricant base stocks. In variousaspects, the difference between the cloud point and pour point for theresulting solvent dewaxed oil and/or for one or more Group II lubricantbase stocks, including one or more bright stocks, formed from thesolvent processed oil, can be 22° C. or less, or 20° C. or less, or 15°C. or less, or 10° C. or less, such as down to about 1° C. ofdifference.

In some alternative aspects, the above solvent processing can beperformed prior to catalytic dewaxing.

Group II Base Stock Products

For deasphalted oils derived from propane, butane, pentane, hexane andhigher or mixtures thereof, the further hydroprocessing (includingcatalytic dewaxing) and potentially solvent processing can be sufficientto form lubricant base stocks with low haze formation (or no hazeformation) and novel compositional properties. Traditional productsmanufactured today with kinematic viscosity of about 32 cSt at 100° C.contain aromatics that are >10% and/or sulfur that is >0.03% of the baseoil.

In various aspects, base stocks produced according to methods describedherein can have a kinematic viscosity of at least 14 cSt, or at least 20cSt, or at least 25 cSt, or at least 30 cSt, or at least 32 cSt at 100°C. and can contain less than 10 wt % aromatics/greater than 90 wt %saturates and less than 0.03% sulfur. Optionally, the saturates contentcan be still higher, such as greater than 95 wt %, or greater than 97 wt%.

Base oils of the compositions described above have further been found toprovide the advantage of being haze free upon initial production andremaining haze free for extended periods of time. This is an advantageover the prior art of high saturates heavy base stocks that wasunexpected.

Additionally, it has been found that these base stocks can be blendedwith additives to form formulated lubricants, such as but not limited tomarine oils, engine oils, greases, paper machine oils, and gear oils.These additives may include, but are not restricted to, detergents,dispersants, antioxidants, viscosity modifiers, and pour pointdepressants. More generally, a formulated lubricating including a basestock produced from a deasphalted oil may additionally contain one ormore of the other commonly used lubricating oil performance additivesincluding but not limited to antiwear agents, dispersants, otherdetergents, corrosion inhibitors, rust inhibitors, metal deactivators,extreme pressure additives, anti-seizure agents, wax modifiers,viscosity index improvers, viscosity modifiers, fluid-loss additives,seal compatibility agents, friction modifiers, lubricity agents,anti-staining agents, chromophoric agents, defoamants, demulsifiers,emulsifiers, densifiers, wetting agents, gelling agents, tackinessagents, colorants, and others. For a review of many commonly usedadditives, see Klamann in Lubricants and Related Products, VerlagChemie, Deerfield Beach, Fla.; ISBN 0-89573-177-0. These additives arecommonly delivered with varying amounts of diluent oil, that may rangefrom 5 weight percent to 50 weight percent.

When so blended, the performance as measured by standard low temperaturetests such as the Mini-Rotary Viscometer (MRV) and Brookfield test hasbeen shown to be superior to formulations blended with traditional baseoils.

It has also been found that the oxidation performance, when blended intoindustrial oils using common additives such as, but not restricted to,defoamants, pour point depressants, antioxidants, rust inhibitors, hasexemplified superior oxidation performance in standard oxidation testssuch as the US Steel Oxidation test compared to traditional base stocks.

Other performance parameters such as interfacial properties, depositcontrol, storage stability, and toxicity have also been examined and aresimilar to or better than traditional base oils.

In addition to being blended with additives, the base stocks describedherein can also be blended with other base stocks to make a base oil.These other base stocks include solvent processed base stocks,hydroprocessed base stocks, synthetic base stocks, base stocks derivedfrom Fisher-Tropsch processes, PAO, and naphthenic base stocks.Additionally or alternately, the other base stocks can include Group Ibase stocks, Group II base stocks, Group III base stocks, Group IV basestocks, and/or Group V base stocks. Additionally or alternately, stillother types of base stocks for blending can include hydrocarbylaromatics, alkylated aromatics, esters (including synthetic and/orrenewable esters), and or other non-conventional or unconventional basestocks. These base oil blends of the inventive base stock and other basestocks can also be combined with additives, such as those mentionedabove, to make formulated lubricants.

Configuration Examples

FIGS. 1 to 3 show examples of using blocked operation and/or partialproduct recycle during lubricant production based on a feed includingdeasphalted resid. In FIGS. 1 to 3, after initial sour stage processing,the hydroprocessed effluent is fractionated to form light neutral, heavyneutral, and brightstock portions. FIG. 1 shows an example of theprocess flow during processing to form light neutral base stock. FIG. 2shows an example of the process flow during processing to form heavyneutral base stock. FIG. 3 shows an example of the process flow duringprocessing to form brightstock.

In FIG. 1, a feed 705 is introduced into a deasphalter 710. Thedeasphalter 710 generates a deasphalted oil 715 and deasphalter rock orresidue 718. The deasphalted oil 715 is then processed in a sourprocessing stage 720. Optionally, a portion 771 of recycled lightneutral base product 762 can be combined with deasphalted oil 715. Sourprocessing stage 720 can include one or more of a deasphalting catalyst,a hydrotreating catalyst, a hydrocracking catalyst, and/or an aromaticsaturation catalyst. The conditions in sour processing stage 720 can beselected to at least reduce the sulfur content of the hydroprocessedeffluent 725 to 20 wppm or less. This can correspond to 15 wt % to 40 wt% conversion of the feed relative to 370° C. Optionally, the amount ofconversion in the sour processing stage 720 can be any convenient higheramount so long as the combined conversion in sour processing stage 720and sweet processing stage 750 is 90 wt % or less.

The hydroprocessed effluent 725 can then be passed into fractionationstage 730 for separation into a plurality of fractions. In the exampleshown in FIG. 1, the hydroprocessed effluent is separated into a lightneutral portion 732, a heavy neutral portion 734, and a brightstockportion 736. To allow for blocked operation, the light neutral portion732 can be sent to corresponding light neutral storage 742, the heavyneutral portion 734 can be sent to corresponding heavy neutral storage744, and the brightstock portion 736 can be sent to correspondingbrightstock storage 746. A lower boiling range fraction 731corresponding to fuels and/or light ends can also be generated byfractionation stage 730. Optionally, fractionation stage can generate aplurality of lower boiling range fractions 731.

FIG. 1 shows an example of the processing system during a light neutralprocessing block. In FIG. 1, the feed 752 to sweet processing stage 750corresponds to a feed derived from light neutral storage 742. The sweetprocessing stage 750 can include at least dewaxing catalyst, andoptionally can further include one or more of hydrocracking catalyst andaromatics saturation catalyst. The dewaxed effluent 755 from sweetprocessing stage 750 can then be passed into a fractionator 760 to formlight neutral base stock product 762. A lower boiling fraction 761corresponding to fuels and/or light ends can also be separated out byfractionator 760. Optionally, a portion of light neutral base stock 762can be recycled. The recycled portion of light neutral base stock 762can be used as a recycled feed portion 771 and/or as a recycled portion772 that is added to light neutral storage 742. Recycling a portion 771for use as part of the feed can be beneficial for increasing thelifetime of the catalysts in sour processing stage 720. Recycling aportion 772 to light neutral storage 742 can be beneficial forincreasing conversion and/or VI.

FIG. 2 shows the same processing configuration during processing of aheavy neutral block. In FIG. 2, the feed 754 to sweet processing stage750 is derived from heavy neutral storage 744. The dewaxed effluent 755from sweet processing stage 750 can be fractionated 760 to form lowerboiling portion 761, heavy neutral base stock product 764, and lightneutral base stock product 762. Because block operation to form a heavyneutral base stock results in production of both a light neutral product762 and a heavy neutral product 764, various optional recycle streamscan also be used. In the example shown in FIG. 2, optional recycleportions 771 and 772 can be used for recycle of the light neutralproduct 762. Additionally, optional recycle portions 781 and 784 can beused for recycle of the heavy neutral product 764. Recycle portions 781and 784 can provide similar benefits to those for recycle portions 771and/or 772.

FIG. 3 shows the same processing configuration during processing of abright stock block. In FIG. 3, the feed 756 to sweet processing stage750 is derived from bright stock storage 746. The dewaxed effluent 755from sweet processing stage 750 can be fractionated 760 to form lowerboiling portion 761, bottoms product 766, heavy neutral base stockproduct 764, and light neutral base stock product 762. Bottoms product766 can then be extracted 790 to form a bright stock product 768. Thearomatic extract 793 produced in extractor 790 can be recycled for use,for example, as part of the feed to deasphalter 710.

Because block operation to form a bright stock results in production ofa bright stock product 768 as well as a light neutral product 762 and aheavy neutral product 764, various optional recycle streams can also beused. In the example shown in FIG. 3, optional recycle portions 771 and772 can be used for recycle of the light neutral product 762, whileoptional recycle portions 781 and 784 can be used for recycle of theheavy neutral product 764. Additionally, optional recycle portions 791and 796 can be used for recycle of the bottoms product 766. Recycleportions 791 and 796 can provide similar benefits to those for recycleportions 771, 772, 781, and/or 784.

Recycle of a portion of the products can also be used in conjunctionwith wide cut processing of a larger portion of the lubricant boilingrange feed to the second stage, such as processing substantially all ofthe feed to the second stage for lubricant production as a wide cutfeed. FIG. 6 shows an example of a configuration for processing of awide cut lubricant feed in the second (sweet) stage, with variousoptional recycle streams. The configuration is similar to theconfiguration shown in FIG. 3. However, instead of using a feed 756derived from feed storage 746 for forming a brightstock, theconfiguration in FIG. 6 uses the bottoms 738 from fractionator 730 asthe feed to the sweet stage 750.

Recycle of intermediate products from the sour stage can also bebeneficial in some circumstances. FIG. 7 shows an example of aconfiguration for block processing to form lubricant products wherevarious recycle options are available within the sour processing stage.Of course, the recycle options shown in FIG. 7 can be used inconjunction with any of the configurations shown in FIGS. 3 to 6.

In FIG. 7, feed 805 is introduced into deasphalter 810. Optionally, aportion of recycled bottoms 893 from fractionator 830 can be included aspart of feed 805. This can generate a deasphalter rock fraction 818 anda deasphalted oil 815. Deasphalted oil 815 can be passed into sourprocessing stage 820, which can include (for example) catalysts fordemetallization, hydrotreating, and hydrocracking. Sour processing stage820 can produce a sour stage effluent 825, which is passed intofractionator 830. Fractionator 830 can generate various feeds forproduction of lubricant boiling range products, such as a light neutralbase stock feed 832 (for storage 842), a heavy neutral base stock feed834 (for storage 844), and a brightstock feed 836 (for storage 846).Optionally, a portion of light neutral base stock feed 832 can berecycled 871 for combination with deasphalted oil 815. Additionally oralternately, a portion of heavy neutral base stock feed 834 canoptionally be recycled 881 for combination with deasphalted oil 815.Additionally or alternately, a portion of brightstock feed 836 canoptionally be recycled 891 for combination with deasphalted oil 815.

After the sour stage, the configuration in FIG. 7 can operate in amanner similar to the configurations shown in FIGS. 3 to 5. In FIG. 7,the block operation of the configuration is shown during a time periodwhen brightstock is being produced. Thus, the feed 856 to the sweetprocessing stage 850 is derived from brightstock storage 846. Theeffluent 855 from sweet processing stage 850 can then be fractionated860 to form, for example, light ends fraction 861, a light neutral basestock product 862, a heavy neutral base stock product 864, and abrightstock product 866. Optionally, the brightstock product 866 can beextracted 890 to form an extracted brightstock product 868.

Example 1—Viscosity and Viscosity Index Relationships

FIG. 4 shows an example of the relationship between processing severity,kinematic viscosity, and viscosity index for lubricant base stocksformed from a deasphalted oil. The data in FIG. 4 corresponds tolubricant base stocks formed from a pentane deasphalted oil at 75 wt %yield on resid feed. The deasphalted oil had a solvent dewaxed VI of75.8 and a solvent dewaxed kinematic viscosity at 100° C. of 333.65.

In FIG. 4, kinematic viscosities (right axis) and viscosity indexes(left axis) are shown as a function of hydroprocessing severity (510°C.+ conversion) for a deasphalted oil processed in a configurationsimilar to FIG. 4. As shown in FIG. 4, increasing the hydroprocessingseverity can provide VI uplift so that deasphalted oil can be converted(after solvent dewaxing) to lubricant base stocks. However, increasingseverity also reduces the kinematic viscosity of the 510° C.+ portion ofthe base stock, which can limit the yield of bright stock. The 370°C.-510° C. portion of the solvent dewaxed product can be suitable forforming light neutral and/or heavy neutral base stocks, while the 510°C.+ portion can be suitable for forming bright stocks and/or heavyneutral base stocks.

Example 2—Variations in Sweet and Sour Hydrocracking

In addition to providing a method for forming Group II base stocks froma challenged feed, the methods described herein can also be used tocontrol the distribution of base stocks formed from a feed by varyingthe amount of conversion performed in sour conditions versus sweetconditions. This is illustrated by the results shown in FIG. 5.

In FIG. 5, the upper two curves show the relationship between the cutpoint used for forming a lubricant base stock of a desired viscosity(bottom axis) and the viscosity index of the resulting base stock (leftaxis). The curve corresponding to the circle data points representsprocessing of a C₅ deasphalted oil using a configuration similar to FIG.6, with all of the hydrocracking occurring in the sour stage. The curvecorresponding to the square data points corresponds to performingroughly half of the hydrocracking conversion in the sour stage and theremaining hydrocracking conversion in the sweet stage (along with thecatalytic dewaxing). The individual data points in each of the uppercurves represent the yield of each of the different base stocks relativeto the amount of feed introduced into the sour processing stage. It isnoted that summing the data points within each curve shows the sametotal yield of base stock, which reflects the fact that the same totalamount of hydrocracking conversion was performed in both types ofprocessing runs. Only the location of the hydrocracking conversion (allsour, or split between sour and sweet) was varied.

The lower pair of curves provides additional information about the samepair of process runs. As for the upper pair of curves, the circle datapoints in the lower pair of curves represent all hydrocracking in thesour stage and the square data points correspond to a split ofhydrocracking between sour and sweet stages. The lower pair of curvesshows the relationship between cut point (bottom axis) and the resultingkinematic viscosity at 100° C. (right axis). As shown by the lower pairof curves, the three cut point represent formation of a light neutralbase stock (5 or 6 cSt), a heavy neutral base stock (10-12 cSt), and abright stock (about 30 cSt). The individual data points for the lowercurves also indicate the pour point of the resulting base stock.

As shown in FIG. 5, altering the conditions under which hydrocracking isperformed can alter the nature of the resulting lubricant base stocks.Performing all of the hydrocracking conversion during the first (sour)hydroprocessing stage can result in higher viscosity index values forthe heavy neutral base stock and bright stock products, while alsoproducing an increased yield of heavy neutral base stock. Performing aportion of the hydrocracking under sweet conditions increased the yieldof light neutral base stock and bright stock with a reduction in heavyneutral base stock yield. Performing a portion of the hydrocrackingunder sweet conditions also reduced the viscosity index values for theheavy neutral base stock and bright stock products. This demonstratesthat the yield of base stocks and/or the resulting quality of basestocks can be altered by varying the amount of conversion performedunder sour conditions versus sweet conditions.

Example 3—Feedstocks and DAOs

Table 1 shows properties of two types of vacuum resid feeds that arepotentially suitable for deasphalting, referred to in this example asResid A and Resid B. Both feeds have an API gravity of less than 6, aspecific gravity of at least 1.0, elevated contents of sulfur, nitrogen,and metals, and elevated contents of carbon residue and n-heptaneinsolubles.

TABLE 1 Resid Feed Properties Resid (566° C.+) Resid A Resid B APIGravity (degrees) 5.4 4.4 Specific Gravity (15° C.) (g/cc) 1.0336 1.0412Total Sulfur (wt %) 4.56 5.03 Nickel (wppm) 43.7 48.7 Vanadium (wppm)114 119 TAN (mg KOH/g) 0.314 0.174 Total Nitrogen (wppm) 4760 4370 BasicNitrogen (wppm) 1210 1370 Carbon Residue (wt %) 24.4 25.8 n-heptaneinsolubles (wt %) 7.68 8.83 Wax (Total—DSC) (wt %) 1.4 1.32 KV @ 100° C.(cSt) 5920 11200 KV @ 135° C. (cSt) 619 988

The resids shown in Table 1 were used to form deasphalted oil. Resid Awas exposed to propane deasphalting (deasphalted oil yield <40%) andpentane deasphalting conditions (deasphalted oil yield ˜65%). Resid Bwas exposed to butane deasphalting conditions (deasphalted oil yield˜75%). Table 2 shows properties of the resulting deasphalted oils.

TABLE 2 Examples of Deasphalted Oils C₃ DAO C₄ DAO C₅ DAO API Gravity(degrees) 22.4 12.9 12.6 Specific Gravity (15° C.) (g/cc) 0.9138 0.97820.9808 Total Sulfur (wt %) 2.01 3.82 3.56 Nickel (wppm) <0.1 5.2 5.3Vanadium (wppm) <0.1 15.6 17.4 Total Nitrogen (wppm) 504 2116 1933 BasicNitrogen (wppm) 203 <N/A> 478 Carbon Residue (wt %) 1.6 8.3 11.0 KV @100° C. (cSt) 33.3 124 172 VI 96 61 <N/A> SimDist (ASTM D2887) ° C.  5wt % 509 490 527 10 wt % 528 515 546 30 wt % 566 568 588 50 wt % 593 608619 70 wt % 623 657 664 90 wt % 675 <N/A> <N/A> 95 wt % 701 <N/A> <N/A>

As shown in Table 2, the higher severity deasphalting provided bypropane deasphalting results in a different quality of deasphalted oilthan the lower severity C₄ and C₅ deasphalting that was used in thisexample. It is noted that the C₃ DAO has a kinematic viscosity @100° C.of less than 35, while the C₄ DAO and C₅ DAO have kinematic viscositiesgreater than 100. The C₃ DAO also generally has properties more similarto a lubricant base stock product, such as a higher API gravity, a lowermetals content/sulfur content/nitrogen content, lower CCR levels, and/ora higher viscosity index.

Example 4—Sour Stage Processing Using Bulk Metal Catalyst

One of the difficulties with processing of feeds based on deasphaltedoils for forming lubricant base stocks is that the feeds have anincreased susceptibility to forming polynuclear aromatics (PNAs) duringprocessing. The tendency to form PNAs can increase with the length ofexposure to sufficiently severe hydroprocessing conditions. As a result,during sour stage processing for removal of contaminants and/orviscosity index uplift, it can be beneficial to use higher activitycatalysts so that the space velocity in the sour stage can be increasedwhile still achieving desired properties for the sour stage effluent.

The impact of using a bulk metal catalyst as part of sour stagehydroprocessing of a feed was investigated by processing a feed in alaboratory scale two reactor configuration. The first reactor includedthe two commercially available demetallization/hydrotreating catalystbeds described in Example 13. In various processing runs, the secondreactor included three different combinations of hydrotreating catalyst.One option for the second reactor catalyst was to use a commerciallyavailable hydrotreating catalyst. In a second option, the commerciallyavailable hydrotreating catalyst was used in conjunction with a firstbulk multimetallic catalyst formed from reactants at least partially inthe solid state, as described above. In a third option, the commerciallyavailable hydrotreating catalyst was used in conjunction with a secondbulk multimetallic catalyst formed from a precursor including organiccomponents, as described above.

Table 3 shows the feed used for the first reactor, and the resultingfirst reactor product that was used as a feed for the second reactor. Itis believed that the feed to the first reactor and the feed to thesecond reactor is representative of the feeds/inputs that would be usedduring formation of a lubricant base stock from high lift deasphaltedoil. During such production, a sour hydrocracking reactor would be usedto further process the output generated from the second reactor. The rawDAO shown in Table 14 corresponds to a deasphalted oil formed by C₅deasphalting.

TABLE 3 Feed to First and Second Reactors of Sour Processing StagePrepared feed to second stage HDT (Optionally including Raw DAO bulkmetal catalyst) Specific gravity at 0.9839 0.9212 15° C. (g/cm³) H, wt %10.76 12.73 S, wppm 34600 726 N, wppm 2562 113 Conradson Carbon 12.11.22 Residue, wt %

After processing the raw DAO from Table 3 in the first reactor to formthe feed for hydrotreatment in the second reactor, the feed to thesecond reactor was processed in the presence of one of the threecatalyst options. The processing conditions included a pressure of 2200psig (˜15.2 MPag) and a hydrogen treat gas rate of 8000 SCF/b (˜1400Nm³/m³). The temperature and LHSV were varied to provide processingconditions 1-5 shown in Table 4.

TABLE 4 Second Reactor Processing Conditions and Product PropertiesCondition 1 2 3 Pressure psig 2200 2200 2200 TGR scf/bbl 8000 8000 8000Gas Flow sccm 128.2 128.2 128.2 Liq Flow cc/hr 5.4 5.4 5.4 Temp C. 343356 371 Temp F. 649.4 672.8 699.8 3 cc supported Sulfur ppm 400 287 144Nitrogen ppm 78.2 60 34.1 Density g/ml 0.8799 0.8803 0.8765 3 ccsupported/ 2 cc bulk cat 1 Sulfur ppm 232 133 45.3 Nitrogen ppm 56 38 15Density g/ml 0.8787 0.8762 0.8701 3 cc supported/ 2 cc bulk cat 2 Sulfurppm 157 76 22 Nitrogen ppm 43 24 7 Density g/ml 0.8760 0.8735 0.8647

As shown in Table 4, the configurations including both the commercialsupported catalyst and a bulk catalyst included more total catalystvolume than the configuration using just the commercially availablesupported catalyst. As a result, the space velocities are different. Asshown in Table 4, both bulk catalysts provided improved activityrelative to using a commercially available supported catalyst. Althoughthe space velocities are different in the examples including both bulkand supported catalyst versus supported catalyst alone, those of skillin the art will recognize that based on a first order model, it is clearthat the bulk catalysts provide superior activity for sulfur removal.Additionally, use of bulk catalyst 2 (formed from a precursor includingan organic component) provides a significant activity advantage over useof bulk catalyst 1.

Example 5—Production of Base Stocks (Including Brightstock) at HighConversion

Another series of processing runs were performed using a C₅ DAO (75 wt %yield) as a feed for lubricant production. The configuration was similarto FIG. 13. Block processing was used for the sweet processing stage.The light neutral, heavy neutral, and brightstock portions wereprocessed under conditions to produce two levels of conversion relativeto 370° C. In a first set of runs, the combined sour stage and sweetstage conversion was 60 wt %. In a second set of runs, the combined sourstage and sweet stage conversion was 82 wt %. It is noted that at highrates of conversion during a single pass, any portions of a lubricantproduct that are recycled could potentially undergo conversion amountsof greater than 70 wt %, or greater than 75 wt %, or greater than 80 wt%, such as up to 90 wt % or more.

Conventionally, conversion of greater than roughly 70 wt % of afeedstock during lubricant product is believed to lead to largereductions in viscosity index for resulting lubricant products. Withoutbeing bound by any particular theory, this is believed to be due in partto conversion of isoparaffins with the feed at elevated levels ofconversion. It has been surprisingly discovered that feeds derived fromhigh yield deasphalted oils (such as deasphalting yields of at least 50wt %) can be undergo greater than 70 wt % conversion without havingsubstantial reductions in VI. This is believed to be related to theunusually high aromatic content of lubricant feeds derived from highyield deasphalted oils.

Table 5 shows results from processing the C₅ DAO feed in this example atconversion amounts of 60 wt % and 82 wt % (combined conversion acrossinitial sour stage and second sweet stage) for production during blockoperation of a light neutral product, a heavy neutral product, and abrightsock product. As shown in Table 5, increasing the combinedconversion results in products with comparable (or potentially higher)viscosity index values, while also generating products withsubstantially reduced pour point values.

TABLE 5 Product properties at varying conversion 82 wt % 60 wt %combined conversion combined conversion (relative to 370° C.) (relativeto 370° C.) Light Neutral VI 106 106 Pour Point (° C.) −64 −34 KV @ 100°C. (cSt) 4.9 4.3 Heavy Neutral VI 100.9 100.5 Pour Point (° C.) −48 −34KV @ 100° C. (cSt) 11.9 12.6 Brightstock VI 109 106.3 Pour Point (° C.)−32 −20 KV @ 100° C. (cSt) 34.6 43.2

Additional Embodiments Embodiment 1

A method for making lubricant base stock, comprising: performing solventdeasphalting, optionally using a C₄₊ solvent, under effective solventdeasphalting conditions on a feedstock having a T5 boiling point of atleast about 370° C. (or at least about 400° C., or at least about 450°C., or at least about 500° C.), the effective solvent deasphaltingconditions producing a yield of deasphalted oil of at least about 50 wt% of the feedstock; hydroprocessing at least a portion of thedeasphalted oil under first effective hydroprocessing conditions to forma hydroprocessed effluent, the hydroprocessing comprising exposing theat least a portion of the deasphalted oil to a mixed metal catalystunder the hydroprocessing conditions, the at least a portion of thedeasphalted oil having an aromatics content of at least about 50 wt %,the hydroprocessed effluent comprising a sulfur content of 300 wppm orless, a nitrogen content of 100 wppm or less, or a combination thereof;separating the hydroprocessed effluent to form at least a fuels boilingrange fraction, a first fraction having a T₅ distillation point of atleast 370° C., and a second fraction having a T₅ distillation point ofat least 370° C., the second fraction having a higher kinematicviscosity at 100° C. than the first fraction; hydroprocessing at least aportion of the first fraction under second effective hydroprocessingconditions, the second effective hydroprocessing conditions comprisingcatalytic dewaxing conditions, to form a first catalytically dewaxedeffluent comprising a 370° C.+ portion having a first kinematicviscosity at 100° C.; and hydroprocessing at least a portion of thesecond fraction under third effective hydroprocessing conditions, thethird effective hydroprocessing conditions comprising catalytic dewaxingconditions, to form a second catalytically dewaxed effluent comprising a370° C.+ portion having a second kinematic viscosity at 100° C. that isgreater than the first kinematic viscosity at 100° C., wherein thesecond effective hydroprocessing conditions are different from the thirdeffective hydroprocessing conditions, and wherein the mixed metalcatalyst comprises a sulfided mixed metal catalyst formed by sulfiding amixed metal catalyst precursor composition, the mixed metal catalystprecursor composition being produced by a) heating a compositioncomprising at least one metal from Group 6 of the Periodic Table of theElements, at least one metal from Groups 8-10 of the Periodic Table ofthe Elements, and a reaction product formed from (i) a first organiccompound containing at least one amine group, and (ii) a second organiccompound separate from said first organic compound and containing atleast one carboxylic acid group to a temperature from about 195° C. toabout 260° C. for a time sufficient for the first and second organiccompounds to form a reaction product in situ that contains an amidemoiety, unsaturated carbon atoms not present in the first or secondorganic compounds, oxygen atoms not present in the first or secondorganic compounds, or a combination thereof; b) heating a compositioncomprising one metal from Group 6 of the Periodic Table of the Elements,at least one metal from Groups 8-10 of the Periodic Table of theElements, and a reaction product formed from (iii) a first organiccompound containing at least one amine group and at least 10 carbonatoms or (iv) a second organic compound containing at least onecarboxylic acid group and at least 10 carbon atoms, but not both (iii)and (iv), wherein the reaction product contains additional unsaturatedcarbon atoms, relative to (iii) the first organic compound or (iv) thesecond organic compound, wherein the metals of the catalyst precursorcomposition are arranged in a crystal lattice, and wherein the reactionproduct is not located within the crystal lattice, to a temperature fromabout 195° C. to about 260° C. for a time sufficient for the first orsecond organic compounds to form a reaction product in situ thatcontains unsaturated carbon atoms not present in the first or secondorganic compounds, oxygen atoms not present in the first or secondorganic compounds, or a combination thereof; or c) heating a compositioncomprising at least one metal from Group 6 of the Periodic Table of theElements, at least one metal from Groups 8-10 of the Periodic Table ofthe Elements, and a pre-formed amide formed from (v) a first organiccompound containing at least one amine group, and (vi) a second organiccompound separate from said first organic compound and containing atleast one carboxylic acid group, to form at least one of additional insitu unsaturated carbon atoms or in situ added oxygen atoms not presentin the first organic compound, the second organic compound, or both, butnot for so long that the pre-formed amide substantially decomposes,thereby forming a catalyst precursor containing at least one of in situformed unsaturated carbon atoms or in situ added oxygen atoms.

Embodiment 2

The method of Embodiment 1, wherein the catalyst precursor compositionis treated first with said first organic compound and second with saidsecond organic compound, or wherein the catalyst precursor compositionis treated first with said second organic compound and second with saidfirst organic compound, or wherein the catalyst precursor composition istreated simultaneously with said first organic compound and with saidsecond organic compound.

Embodiment 3

The method of Embodiment 1 or 2, wherein said at least one metal fromGroup 6 is Mo, W, or a combination thereof, and wherein said at leastone metal from Groups 8-10 is Co, Ni, or a combination thereof.

Embodiment 4

The process of any of Embodiments 1 to 3, wherein the mixed metalcatalyst precursor composition is a bulk metal hydroprocessing catalystprecursor composition consisting essentially of the reaction product, anoxide form of the at least one metal from Group 6, an oxide form of theat least one metal from Groups 8-10, and optionally about 20 wt % orless of a binder.

Embodiment 5

A method for making lubricant base stock, comprising: performing solventdeasphalting, optionally using a C₄₊ solvent, under effective solventdeasphalting conditions on a feedstock having a T5 boiling point of atleast about 370° C. (or at least about 400° C., or at least about 450°C., or at least about 500° C.), the effective solvent deasphaltingconditions producing a yield of deasphalted oil of at least about 50 wt% of the feedstock; hydroprocessing at least a portion of thedeasphalted oil under first effective hydroprocessing conditions to forma hydroprocessed effluent, the hydroprocessing comprising exposing theat least a portion of the deasphalted oil to a bulk multimetalliccatalyst under the hydroprocessing conditions, the at least a portion ofthe deasphalted oil having an aromatics content of at least about 50 wt%, the hydroprocessed effluent comprising a sulfur content of 300 wppmor less, a nitrogen content of 100 wppm or less, or a combinationthereof; separating the hydroprocessed effluent to form at least a fuelsboiling range fraction, a first fraction having a T₅ distillation pointof at least 370° C., and a second fraction having a T₅ distillationpoint of at least 370° C., the second fraction having a higher kinematicviscosity at 100° C. than the first fraction; hydroprocessing at least aportion of the first fraction under second effective hydroprocessingconditions, the second effective hydroprocessing conditions comprisingcatalytic dewaxing conditions, to form a first catalytically dewaxedeffluent comprising a 370° C.+ portion having a first kinematicviscosity at 100° C.; and hydroprocessing at least a portion of thesecond fraction under third effective hydroprocessing conditions, thethird effective hydroprocessing conditions comprising catalytic dewaxingconditions, to form a second catalytically dewaxed effluent comprising a370° C.+ portion having a second kinematic viscosity at 100° C. that isgreater than the first kinematic viscosity at 100° C., wherein thesecond effective hydroprocessing conditions are different from the thirdeffective hydroprocessing conditions, and wherein the bulk multimetalliccatalyst comprises of at least one Group VIII non-noble metal and atleast two Group VIB metals and wherein the ratio of Group VIB metal toGroup VIII non-noble metal is from about 10:1 to about 1:10.

Embodiment 6

The method of Embodiment 5, wherein the Group VIII non-noble metal isselected from Ni and Co and the Group VIB metals are selected from Moand W.

Embodiment 7

The method of Embodiment 5 or 6, wherein the bulk multimetallic isrepresented by the formula: (X)_(b)(Mo)_(c)(W)_(d)O_(x), and wherein Xis a Group VIII non-noble metal, and the molar ratio of b:(c+d) is 0.5/1to 3/1.

Embodiment 8

The method of any of Embodiments 5 to 7, wherein the molar ratio ofb:(c+d) is 0.75/1 to 1.5/1; or wherein the molar ratio of c:dis >0.01/1; or a combination thereof.

Embodiment 9

The method of any of Embodiments 5 to 8 wherein the bulk multimetalliccatalyst is essentially an amorphous material having a unique X-raydiffraction pattern showing crystalline peaks at d=2.53 Angstroms andd=1.70 Angstroms; or wherein the bulk multimetallic catalyst alsocontains an acid function; or a combination thereof.

Embodiment 10

The method of any of the above embodiments, wherein the second effectivehydroprocessing conditions further comprise hydrocracking conditions andthe third effective hydroprocessing conditions further comprisehydrocracking conditions, the second effective hydroprocessingconditions and third effective hydroprocessing conditions beingdifferent based on a difference in at least one of a hydrocrackingpressure, a hydrocracking temperature, a dewaxing pressure, and adewaxing temperature.

Embodiment 11

The method of any of the above embodiments, further comprising at leastone of: a) solvent extracting at least a portion of the secondcatalytically dewaxed effluent to form a solvent processed effluent, orb) solvent dewaxing at least a portion of the second catalyticallydewaxed effluent to form a solvent processed effluent, wherein thesolvent processed effluent comprises a T5 distillation point of at least482° C., a VI of at least 80, a pour point of −6° C. or less, and acloud point of −2° C. or less (or optionally −5° C. or less).

Embodiment 12

The method of any of the above embodiments, wherein the process furthercomprises recycling at least a portion of a) the third fraction, b) thefourth fraction, c) the first catalytically dewaxed effluent, d) thefirst fraction, e) the second fraction, or c) a combination of aplurality of a)-e), as part of i) the at least a portion of thedeasphalted oil, ii) the at least a portion of the first fraction, iii)the at least a portion of the second fraction, or iv) a combination of aplurality of i), ii), and iii).

Embodiment 13

The method of any of the above embodiments, wherein the hydroprocessingat least a portion of the first fraction and the hydroprocessing atleast a portion of the second fraction comprises block operation of aprocessing system.

Embodiment 14

The method of any of the above embodiments, wherein at least one of thesecond effective hydroprocessing conditions and the third effectivehydroprocessing conditions further comprises performing aromaticsaturation.

Embodiment 15

The method of any of the above embodiments, wherein the yield ofdeasphalted oil is at least 55 wt %, or at least 60 wt %, or at least 65wt %, or at least 70 wt %, or at least 75 wt %; or wherein thedeasphalted oil has an aromatics content of at least 55 wt %, or atleast 60 wt %, or at least 65 wt %, or at least 70 wt % based on aweight of the deasphalted oil; or a combination thereof.

Embodiment 16

The method of any of the above embodiments, wherein the C₄₊ solventcomprises a C₅₊ solvent, a mixture of two or more C₅ isomers, or acombination thereof.

Embodiment 17

The method of any of the above embodiments, wherein a combinedconversion of the feedstock across the first effective hydroprocessingconditions and the second effective hydroprocessing conditions is atleast 70 wt % relative to 370° C., or at least 75 wt %, or at least 80wt %, the second catalytically dewaxed effluent having a viscosity indexof at least 90, or at least 100; or wherein a combined conversion of thefeedstock across the first effective hydroprocessing conditions and thethird effective hydroprocessing conditions is at least 70 wt % relativeto 370° C., or at least 75 wt %, or at least 80 wt %, the thirdcatalytically dewaxed effluent and/or the fourth fraction having aviscosity index of at least 90, or at least 100; or a combinationthereof.

Embodiment 18

The method of any of the above embodiments, wherein separating thehydroprocessed effluent further comprises forming an additional fractionhaving a T₅ distillation point of at least 370° C., the method furthercomprising: hydroprocessing at least a portion of the additionalfraction under third effective hydroprocessing conditions, the thirdeffective hydroprocessing conditions comprising catalytic dewaxingconditions, to form a third catalytically dewaxed effluent comprising a370° C.+ portion having a kinematic viscosity at 100° C. of 3.5 cSt ormore.

Embodiment 19

The method of any of the above embodiments, wherein at least a portionof the first fraction, at least a portion of the second fraction, atleast a portion of the first catalytically dewaxed effluent, at least aportion of the second catalytically dewaxed effluent, or a combinationthereof is used as a feed for a steam cracker; or wherein at least aportion of the second catalytically dewaxed effluent is used as anasphalt blend component.

Embodiment 20

A system for producing a lubricant boiling range product, comprising: asolvent deasphalting unit comprising a deasphalting inlet and adeasphalting outlet; a first hydroprocessing stage comprising a firsthydroprocessing inlet and a first hydroprocessing outlet, the firsthydroprocessing inlet being in fluid communication with the deasphaltingoutlet, the first hydroprocessing stage further comprising a sulfidedmixed metal catalyst, a bulk multimetallic catalyst, or a combinationthereof; a first separation stage comprising a first separation inletand a plurality of first separation outlets, the first separation inletbeing in fluid communication with the first stage outlet; a plurality ofstorage tanks in fluid communication with the plurality of firstseparation outlets; a second hydroprocessing stage comprising a secondhydroprocessing inlet and a second hydroprocessing outlet, the secondhydroprocessing inlet being in intermittent fluid communication with theplurality of storage tanks; and a second separation stage comprising asecond separation inlet and a plurality of second separation outlets,the second separation inlet being in fluid communication with the secondhydroprocessing outlet, wherein a) the deasphalting inlet is in fluidcommunication with at least one separation outlet of the plurality offirst separation outlets, b) the deasphalting inlet is in fluidcommunication with at least one of the plurality of storage tanks, c)the deasphalting outlet is in fluid communication with at least one ofthe plurality of second separation outlets, or d) a combination thereof.

Embodiment 21

The system of Embodiment 20, wherein the system further comprises asolvent extraction stage in fluid communication with one or more of theplurality of second separation outlets.

Embodiment 22

The system of Embodiment 20 or 21, wherein the sulfided mixed metalcatalyst comprises a catalyst formed by sulfiding a mixed metal catalystprecursor composition, the mixed metal catalyst precursor compositionbeing produced by a) heating a composition comprising at least one metalfrom Group 6 of the Periodic Table of the Elements, at least one metalfrom Groups 8-10 of the Periodic Table of the Elements, and a reactionproduct formed from (i) a first organic compound containing at least oneamine group, and (ii) a second organic compound separate from said firstorganic compound and containing at least one carboxylic acid group to atemperature from about 195° C. to about 260° C. for a time sufficientfor the first and second organic compounds to form a reaction product insitu that contains an amide moiety, unsaturated carbon atoms not presentin the first or second organic compounds, oxygen atoms not present inthe first or second organic compounds, or a combination thereof; b)heating a composition comprising one metal from Group 6 of the PeriodicTable of the Elements, at least one metal from Groups 8-10 of thePeriodic Table of the Elements, and a reaction product formed from (iii)a first organic compound containing at least one amine group and atleast 10 carbon atoms or (iv) a second organic compound containing atleast one carboxylic acid group and at least 10 carbon atoms, but notboth (iii) and (iv), wherein the reaction product contains additionalunsaturated carbon atoms, relative to (iii) the first organic compoundor (iv) the second organic compound, wherein the metals of the catalystprecursor composition are arranged in a crystal lattice, and wherein thereaction product is not located within the crystal lattice, to atemperature from about 195° C. to about 260° C. for a time sufficientfor the first or second organic compounds to form a reaction product insitu that contains unsaturated carbon atoms not present in the first orsecond organic compounds, oxygen atoms not present in the first orsecond organic compounds, or a combination thereof; or c) heating acomposition comprising at least one metal from Group 6 of the PeriodicTable of the Elements, at least one metal from Groups 8-10 of thePeriodic Table of the Elements, and a pre-formed amide formed from (v) afirst organic compound containing at least one amine group, and (vi) asecond organic compound separate from said first organic compound andcontaining at least one carboxylic acid group, to form at least one ofadditional in situ unsaturated carbon atoms or in situ added oxygenatoms not present in the first organic compound, the second organiccompound, or both, but not for so long that the pre-formed amidesubstantially decomposes, thereby forming a catalyst precursorcontaining at least one of in situ formed unsaturated carbon atoms or insitu added oxygen atoms.

Embodiment 23

The system of Embodiment 20 or 21, wherein the bulk multimetalliccatalyst comprises of at least one Group VIII non-noble metal and atleast two Group VIB metals and wherein the ratio of Group VIB metal toGroup VIII non-noble metal is from about 10:1 to about 1:10.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present invention,including all features which would be treated as equivalents thereof bythose skilled in the art to which the invention pertains.

The present invention has been described above with reference tonumerous embodiments and specific examples. Many variations will suggestthemselves to those skilled in this art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims.

1. A method for making lubricant base stock, comprising: performingsolvent deasphalting, optionally using a C₄₊ solvent, under effectivesolvent deasphalting conditions on a feedstock having a T5 boiling pointof at least about 370° C., the effective solvent deasphalting conditionsproducing a yield of deasphalted oil of at least about 50 wt % of thefeedstock; hydroprocessing at least a portion of the deasphalted oilunder first effective hydroprocessing conditions to form ahydroprocessed effluent, the hydroprocessing comprising exposing the atleast a portion of the deasphalted oil to a mixed metal catalyst underthe hydroprocessing conditions, the at least a portion of thedeasphalted oil having an aromatics content of at least about 50 wt %,the hydroprocessed effluent comprising a sulfur content of 300 wppm orless, a nitrogen content of 100 wppm or less, or a combination thereof;separating the hydroprocessed effluent to form at least a fuels boilingrange fraction, a first fraction having a T₅ distillation point of atleast 370° C., and a second fraction having a T₅ distillation point ofat least 370° C., the second fraction having a higher kinematicviscosity at 100° C. than the first fraction; hydroprocessing at least aportion of the first fraction under second effective hydroprocessingconditions, the second effective hydroprocessing conditions comprisingcatalytic dewaxing conditions, to form a first catalytically dewaxedeffluent comprising a 370° C.+ portion having a first kinematicviscosity at 100° C.; and hydroprocessing at least a portion of thesecond fraction under third effective hydroprocessing conditions, thethird effective hydroprocessing conditions comprising catalytic dewaxingconditions, to form a second catalytically dewaxed effluent comprising a370° C.+ portion having a second kinematic viscosity at 100° C. that isgreater than the first kinematic viscosity at 100° C., wherein thesecond effective hydroprocessing conditions are different from the thirdeffective hydroprocessing conditions, and wherein the mixed metalcatalyst comprises a sulfided mixed metal catalyst formed by sulfiding amixed metal catalyst precursor composition, the mixed metal catalystprecursor composition being produced by a) heating a compositioncomprising at least one metal from Group 6 of the Periodic Table of theElements, at least one metal from Groups 8-10 of the Periodic Table ofthe Elements, and a reaction product formed from (i) a first organiccompound containing at least one amine group, and (ii) a second organiccompound separate from said first organic compound and containing atleast one carboxylic acid group to a temperature from about 195° C. toabout 260° C. for a time sufficient for the first and second organiccompounds to form a reaction product in situ that contains an amidemoiety, unsaturated carbon atoms not present in the first or secondorganic compounds, oxygen atoms not present in the first or secondorganic compounds, or a combination thereof; b) heating a compositioncomprising one metal from Group 6 of the Periodic Table of the Elements,at least one metal from Groups 8-10 of the Periodic Table of theElements, and a reaction product formed from (iii) a first organiccompound containing at least one amine group and at least 10 carbonatoms or (iv) a second organic compound containing at least onecarboxylic acid group and at least 10 carbon atoms, but not both (iii)and (iv), wherein the reaction product contains additional unsaturatedcarbon atoms, relative to (iii) the first organic compound or (iv) thesecond organic compound, wherein the metals of the catalyst precursorcomposition are arranged in a crystal lattice, and wherein the reactionproduct is not located within the crystal lattice, to a temperature fromabout 195° C. to about 260° C. for a time sufficient for the first orsecond organic compounds to form a reaction product in situ thatcontains unsaturated carbon atoms not present in the first or secondorganic compounds, oxygen atoms not present in the first or secondorganic compounds, or a combination thereof; or c) heating a compositioncomprising at least one metal from Group 6 of the Periodic Table of theElements, at least one metal from Groups 8-10 of the Periodic Table ofthe Elements, and a pre-formed amide formed from (v) a first organiccompound containing at least one amine group, and (vi) a second organiccompound separate from said first organic compound and containing atleast one carboxylic acid group, to form at least one of additional insitu unsaturated carbon atoms or in situ added oxygen atoms not presentin the first organic compound, the second organic compound, or both, butnot for so long that the pre-formed amide substantially decomposes,thereby forming a catalyst precursor containing at least one of in situformed unsaturated carbon atoms or in situ added oxygen atoms.
 2. Themethod of claim 1, wherein the catalyst precursor composition is treatedfirst with said first organic compound and second with said secondorganic compound, or wherein the catalyst precursor composition istreated first with said second organic compound and second with saidfirst organic compound, or wherein the catalyst precursor composition istreated simultaneously with said first organic compound and with saidsecond organic compound.
 3. The method of claim 1, wherein said at leastone metal from Group 6 is Mo, W, or a combination thereof, and whereinsaid at least one metal from Groups 8-10 is Co, Ni, or a combinationthereof.
 4. The process of claim 1, wherein the mixed metal catalystprecursor composition is a bulk metal hydroprocessing catalyst precursorcomposition consisting essentially of the reaction product, an oxideform of the at least one metal from Group 6, an oxide form of the atleast one metal from Groups 8-10, and optionally about 20 wt % or lessof a binder.
 5. The method of claim 1, wherein the second effectivehydroprocessing conditions further comprise hydrocracking conditions andthe third effective hydroprocessing conditions further comprisehydrocracking conditions, the second effective hydroprocessingconditions and third effective hydroprocessing conditions beingdifferent based on a difference in at least one of a hydrocrackingpressure, a hydrocracking temperature, a dewaxing pressure, and adewaxing temperature.
 6. The method of claim 1, further comprising atleast one of: a) solvent extracting at least a portion of the secondcatalytically dewaxed effluent to form a solvent processed effluent, orb) solvent dewaxing at least a portion of the second catalyticallydewaxed effluent to form a solvent processed effluent, wherein thesolvent processed effluent comprises a T5 distillation point of at least482° C., a VI of at least 80, a pour point of −6° C. or less, and acloud point of −2° C. or less.
 7. The method of claim 1, wherein theprocess further comprises recycling at least a portion of a) the thirdfraction, b) the fourth fraction, c) the first catalytically dewaxedeffluent, d) the first fraction, e) the second fraction, or f) acombination of a plurality of a)-e), as part of i) the at least aportion of the deasphalted oil, ii) the at least a portion of the firstfraction, iii) the at least a portion of the second fraction, or iv) acombination of a plurality of i), ii), and iii).
 8. The method of claim1, wherein the hydroprocessing at least a portion of the first fractionand the hydroprocessing at least a portion of the second fractioncomprises block operation of a processing system.
 9. The method of claim1, wherein at least one of the second effective hydroprocessingconditions and the third effective hydroprocessing conditions furthercomprises performing aromatic saturation.
 10. The method of claim 1,wherein the yield of deasphalted oil is at least 55 wt %; or wherein thedeasphalted oil has an aromatics content of at least 55 wt % based on aweight of the deasphalted oil; or a combination thereof.
 11. The methodof claim 1, wherein the C₄₊ solvent comprises a C₅₊ solvent, a mixtureof two or more C₅ isomers, or a combination thereof.
 12. The method ofclaim 1, wherein a combined conversion of the feedstock across the firsteffective hydroprocessing conditions and the second effectivehydroprocessing conditions is at least 70 wt % relative to 370° C., thesecond catalytically dewaxed effluent having a viscosity index of atleast
 90. 13. The method of claim 12, wherein a combined conversion ofthe feedstock across the first effective hydroprocessing conditions andthe third effective hydroprocessing conditions is at least 70 wt %relative to 370° C., the third catalytically dewaxed effluent and/or thefourth fraction having a viscosity index of at least
 90. 14. The methodof claim 1, wherein at least a portion of the first fraction, at least aportion of the second fraction, at least a portion of the firstcatalytically dewaxed effluent, at least a portion of the secondcatalytically dewaxed effluent, or a combination thereof is used as afeed for a steam cracker.
 15. The method of claim 1, wherein at least aportion of the second catalytically dewaxed effluent is used as anasphalt blend component.
 16. The method of claim 1, wherein separatingthe hydroprocessed effluent further comprises forming an additionalfraction having a T₅ distillation point of at least 370° C., the methodfurther comprising: hydroprocessing at least a portion of the additionalfraction under third effective hydroprocessing conditions, the thirdeffective hydroprocessing conditions comprising catalytic dewaxingconditions, to form a third catalytically dewaxed effluent comprising a370° C.+ portion having a kinematic viscosity at 100° C. of 3.5 cSt ormore.
 17. A method for making lubricant base stock, comprising:performing solvent deasphalting, optionally using a C₄₊ solvent, undereffective solvent deasphalting conditions on a feedstock having a T5boiling point of at least about 370° C., the effective solventdeasphalting conditions producing a yield of deasphalted oil of at leastabout 50 wt % of the feedstock; hydroprocessing at least a portion ofthe deasphalted oil under first effective hydroprocessing conditions toform a hydroprocessed effluent, the hydroprocessing comprising exposingthe at least a portion of the deasphalted oil to a bulk multimetalliccatalyst under the hydroprocessing conditions, the at least a portion ofthe deasphalted oil having an aromatics content of at least about 50 wt%, the hydroprocessed effluent comprising a sulfur content of 300 wppmor less, a nitrogen content of 100 wppm or less, or a combinationthereof; separating the hydroprocessed effluent to form at least a fuelsboiling range fraction, a first fraction having a T₅ distillation pointof at least 370° C., and a second fraction having a T₅ distillationpoint of at least 370° C., the second fraction having a higher kinematicviscosity at 100° C. than the first fraction; hydroprocessing at least aportion of the first fraction under second effective hydroprocessingconditions, the second effective hydroprocessing conditions comprisingcatalytic dewaxing conditions, to form a first catalytically dewaxedeffluent comprising a 370° C.+ portion having a first kinematicviscosity at 100° C.; and hydroprocessing at least a portion of thesecond fraction under third effective hydroprocessing conditions, thethird effective hydroprocessing conditions comprising catalytic dewaxingconditions, to form a second catalytically dewaxed effluent comprising a370° C.+ portion having a second kinematic viscosity at 100° C. that isgreater than the first kinematic viscosity at 100° C., wherein thesecond effective hydroprocessing conditions are different from the thirdeffective hydroprocessing conditions, and wherein the bulk multimetalliccatalyst comprises of at least one Group VIII non-noble metal and atleast two Group VIB metals and wherein the ratio of Group VIB metal toGroup VIII non-noble metal is from about 10:1 to about 1:10.
 18. Themethod of claim 17, wherein the Group VIII non-noble metal is selectedfrom Ni and Co and the Group VIB metals are selected from Mo and W. 19.The method of claim 17, wherein the bulk multimetallic is represented bythe formula:(X)_(b)(Mo)c(W)_(d)O_(x) wherein X is a Group VIII non-noble metal, andthe molar ratio of b:(c+d) is 0.5/1 to 3/1.
 20. The method of claim 19,wherein the molar ratio of b:(c+d) is 0.75/1 to 1.5/1.
 21. The method ofclaim 19, wherein the molar ratio of c:d is >0.01/1.
 22. The method ofclaim 17 wherein the bulk multimetallic catalyst is essentially anamorphous material having a unique X-ray diffraction pattern showingcrystalline peaks at d=2.53 Angstroms and d=1.70 Angstroms.
 23. Themethod of claim 17 wherein the bulk multimetallic catalyst also containsan acid function.
 24. The method of claim 17, wherein the secondeffective hydroprocessing conditions further comprise hydrocrackingconditions and the third effective hydroprocessing conditions furthercomprise hydrocracking conditions, the second effective hydroprocessingconditions and third effective hydroprocessing conditions beingdifferent based on a difference in at least one of a hydrocrackingpressure, a hydrocracking temperature, a dewaxing pressure, and adewaxing temperature.
 25. The method of claim 17, further comprising atleast one of: a) solvent extracting at least a portion of the secondcatalytically dewaxed effluent to form a solvent processed effluent, orb) solvent dewaxing at least a portion of the second catalyticallydewaxed effluent to form a solvent processed effluent, wherein thesolvent processed effluent comprises a T5 distillation point of at least482° C., a VI of at least 80, a pour point of −6° C. or less, and acloud point of −2° C. or less.
 26. The method of claim 17, wherein theprocess further comprises recycling at least a portion of a) the thirdfraction, b) the fourth fraction, c) the first catalytically dewaxedeffluent, d) the first fraction, e) the second fraction, or f) acombination of a plurality of a)-e), as part of i) the at least aportion of the deasphalted oil, ii) the at least a portion of the firstfraction, iii) the at least a portion of the second fraction, or iv) acombination of a plurality of i), ii), and iii).
 27. The method of claim17, wherein at least a portion of the first fraction, at least a portionof the second fraction, at least a portion of the first catalyticallydewaxed effluent, at least a portion of the second catalytically dewaxedeffluent, or a combination thereof is used as a feed for a steamcracker; or wherein at least a portion of the second catalyticallydewaxed effluent is used as an asphalt blend component.
 28. The methodof claim 17, wherein separating the hydroprocessed effluent furthercomprises forming an additional fraction having a T₅ distillation pointof at least 370° C., the method further comprising: hydroprocessing atleast a portion of the additional fraction under third effectivehydroprocessing conditions, the third effective hydroprocessingconditions comprising catalytic dewaxing conditions, to form a thirdcatalytically dewaxed effluent comprising a 370° C.+ portion having akinematic viscosity at 100° C. of 3.5 cSt or more.
 29. A system forproducing a lubricant boiling range product, comprising: a solventdeasphalting unit comprising a deasphalting inlet and a deasphaltingoutlet; a first hydroprocessing stage comprising a first hydroprocessinginlet and a first hydroprocessing outlet, the first hydroprocessinginlet being in fluid communication with the deasphalting outlet, thefirst hydroprocessing stage further comprising a sulfided mixed metalcatalyst, a bulk multimetallic catalyst, or a combination thereof; afirst separation stage comprising a first separation inlet and aplurality of first separation outlets, the first separation inlet beingin fluid communication with the first stage outlet; a plurality ofstorage tanks in fluid communication with the plurality of firstseparation outlets; a second hydroprocessing stage comprising a secondhydroprocessing inlet and a second hydroprocessing outlet, the secondhydroprocessing inlet being in intermittent fluid communication with theplurality of storage tanks; and a second separation stage comprising asecond separation inlet and a plurality of second separation outlets,the second separation inlet being in fluid communication with the secondhydroprocessing outlet, wherein a) the deasphalting inlet is in fluidcommunication with at least one separation outlet of the plurality offirst separation outlets, b) the deasphalting inlet is in fluidcommunication with at least one of the plurality of storage tanks, c)the deasphalting outlet is in fluid communication with at least one ofthe plurality of second separation outlets, or d) a combination thereof.30. The system of claim 29, wherein the system further comprises asolvent extraction stage in fluid communication with one or more of theplurality of second separation outlets.
 31. The system of claim 29,wherein the sulfided mixed metal catalyst comprises a catalyst formed bysulfiding a mixed metal catalyst precursor composition, the mixed metalcatalyst precursor composition being produced by a) heating acomposition comprising at least one metal from Group 6 of the PeriodicTable of the Elements, at least one metal from Groups 8-10 of thePeriodic Table of the Elements, and a reaction product formed from (i) afirst organic compound containing at least one amine group, and (ii) asecond organic compound separate from said first organic compound andcontaining at least one carboxylic acid group to a temperature fromabout 195° C. to about 260° C. for a time sufficient for the first andsecond organic compounds to form a reaction product in situ thatcontains an amide moiety, unsaturated carbon atoms not present in thefirst or second organic compounds, oxygen atoms not present in the firstor second organic compounds, or a combination thereof; b) heating acomposition comprising one metal from Group 6 of the Periodic Table ofthe Elements, at least one metal from Groups 8-10 of the Periodic Tableof the Elements, and a reaction product formed from (iii) a firstorganic compound containing at least one amine group and at least 10carbon atoms or (iv) a second organic compound containing at least onecarboxylic acid group and at least 10 carbon atoms, but not both (iii)and (iv), wherein the reaction product contains additional unsaturatedcarbon atoms, relative to (iii) the first organic compound or (iv) thesecond organic compound, wherein the metals of the catalyst precursorcomposition are arranged in a crystal lattice, and wherein the reactionproduct is not located within the crystal lattice, to a temperature fromabout 195° C. to about 260° C. for a time sufficient for the first orsecond organic compounds to form a reaction product in situ thatcontains unsaturated carbon atoms not present in the first or secondorganic compounds, oxygen atoms not present in the first or secondorganic compounds, or a combination thereof; or c) heating a compositioncomprising at least one metal from Group 6 of the Periodic Table of theElements, at least one metal from Groups 8-10 of the Periodic Table ofthe Elements, and a pre-formed amide formed from (v) a first organiccompound containing at least one amine group, and (vi) a second organiccompound separate from said first organic compound and containing atleast one carboxylic acid group, to form at least one of additional insitu unsaturated carbon atoms or in situ added oxygen atoms not presentin the first organic compound, the second organic compound, or both, butnot for so long that the pre-formed amide substantially decomposes,thereby forming a catalyst precursor containing at least one of in situformed unsaturated carbon atoms or in situ added oxygen atoms.
 32. Thesystem of claim 29, wherein the bulk multimetallic catalyst comprises ofat least one Group VIII non-noble metal and at least two Group VIBmetals and wherein the ratio of Group VIB metal to Group VIII non-noblemetal is from about 10:1 to about 1:10.